Process for polymerizing propylene by using a novel metallocene catalyst

ABSTRACT

A process for polymerizing propylene utilizes a metallocene catalyst component of the formula (I)    is a C2-6 hydrocarbon, R2 is a C6-16 aryl group, X1 and X2 are each a halogen atom and Y is a divalent hydrocarbon or a divalent silicon-containing group. Propylene polymers produced thereby have such properties that the triad tacticity of propylene units is high, the proportion of inversely inserted units based on the 2,1-insertion of propylene monomer is in a specific range and the intrinsic viscosity ( eta ), as measured in decahydronaphthalene at 135 DEG  C., is in a specific range.

This is a division of application Ser. No. 08/474,658 filed Jun. 7,1995; now U.S. Pat. No. 5,658,997 which is a division of applicationSer. No. 08/255,706, filed Jun. 7, 1994 now abandoned.

FIELD OF THE INVENTION

The present invention relates to a novel transition metal compound, anolefin polymerization catalyst component comprising the transition metalcompound, an olefin polymerization catalyst containing the catalystcomponent and a process for olefin polymerization using the olefinpolymerization catalyst. The invention also relates to a propylenehomopolymer, a propylene copolymer and a propylene elastomer, all havinga high triad tacticity of the propylene units chain, and low in anamount of inversely inserted propylene units.

BACKGROUND OF THE INVENTION

A well known homogeneous catalyst is, for example, so-called Kaminskycatalyst. Use of this Kaminsky catalyst produces a polymer having anextremely high polymerization activity and a narrow molecular weightdistribution.

Of the Kaminsky catalysts, ethylenebis(indenyl)zirconium dichloride andethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride are known astransition metal compounds for preparing isotactic polyolefins, asdescribed in Japanese Patent Laid-Open Publication No. 130314/1986.However, polyolefins prepared by the use of these catalysts generallyhave a low stereoregularity and a low molecular weight. As a process forpreparing polyolefins of high stereoregularity and high molecular weightusing these catalyst, there is a process in which the polymerization isconducted at a low temperature, but this process has a problem of lowpolymerization activity.

It is known that use of hafnium compounds in place of the zirconiumcompounds makes it possible to prepare a polymer having high molecularweight, as described in "Journal of Molecular Catalysis", 56 (1989), pp.237-247, but this process also has a problem of low polymerizationactivity. Further, dimethylsilyl bissubstituted cyclopentadienylzirconium dichloride is also known as described in Japanese PatentLaid-Open Publication No. 301704/1989 and "Polymer Preprints", Japan,vol. 39, No. 6, pp. 1,614-1,616 (1990), but this compound is notsatisfactory in all of polymerization activity, and stereoregularity andmolecular weight of polymers obtained.

In order to solve these problems, various proposals have been made. Forexample, Japanese Patent Laid-Open Publication 268307/1993 describes anolefin polymerization catalyst formed from a metallocene compoundrepresented by the following formula and aluminoxane as a catalystcapable of preparing a high molecular polyolefin. ##STR2##

Further, EP 0 530 648 A1 describes an olefin polymerization catalystformed from a metallocene compound represented by the following formulaand aluminoxane. ##STR3## wherein A is a lower alkyl group.

However, the stereoregularity and the molecular weight of the polyolefinobtained by the use of these catalysts are not always satisfactorily,and the amount of inversely inserted units is still too large.

Moreover, a catalyst component (wherein, A is a phenyl group or naphthylgroup in the aforementioned metallocene compound) is published fromHOECHST AKTIENGESELLSCHAFT at 40 YEARS ZIEGLER CATALYST IN HONOR OF KARLZIEGER AND WORKSHOP (SEP. 1-3, 1993).

Furthermore, EP 0 576 970 A1 describes an olefin polymerization catalystformed from a metallocene compound represented by the following formulaand an aluminoxane. ##STR4## wherein M¹ is a transition metal atom, R¹and R² are each a holagen atom, etc., R³ is an alkyl group of 1 to 10carbon atoms, etc., R⁴ to R¹² are each an alkyl group of 1 to 10 carbonatoms etc., R¹³ is a hydrocarbon group or a silicon containing group.

However, the stereoregularity of the polyolefin obtained by the use ofthese catalysts are not always satisfactorily, and the amount ofinversely inserted units is still too large.

In the light of such prior arts as described above, the presentinventors have found that polymerization activity of the catalystcomponent comprising the aforementioned transition metal compound isdepending upon the kind of substituent on the indenyl group, and variedmarkedly in the stereoregularity and the amount of the inverselyinserted units of the resulting polyolefin. Further, the inventors havealso found that the transition metal compound having indenyl groupscontaining a specific substituent as a ligand is excellent olefinpolymerization activity, and is capable of giving an olefinpolymerization catalyst which provides an olefin polymer having highstereoregularity and low in the amount of inversely inserted units.

Propylene polymers, especially propylene homopolymers, have been appliedto various uses such as industrial parts, containers, films and nonwovenfabrics, because of their excellent rigidity, surface hardness, heatresistance, glossiness and transparency.

However, the conventional propylene homopolymer is not always sufficientin transparency, impact resistance, etc. for some uses, and thereforethe advent of a propylene polymer excellent in rigidity, heatresistance, surface hardness, glossiness, transparency and impactstrength is desired.

Moreover, the physical properties of the copolymers of propylene and anα-olefin other than propylene vary depending on composition thereof, andhence the copolymers are generally distinguishable from each otherbordering the monomer content derived from the α-olefin other thanpropylene of 5% by mol.

Propylene copolymers containing monomer units derived from α-olefinother than propylene in an amount of less than 5% by mol have beenapplied to various uses such as containers and packaging materials(e.g., films), because of their excellent rigidity, surface hardness,heat resistance, transparency and heat-sealing property. However, whenthe copolymer is used as a film, the resulting film is not alwayssufficient in transparency, heat-sealing property, anti-blockingproperty, anti-bleedout property and impact strength. Therefore, apropylene copolymer further improved in transparency, rigidity, surfacehardness, heat resistance and heat-sealing property, and havingexcellent anti-blocking property, anti-bleedout property and impactstrength is desired.

In contrast, propylene copolymers containing monomer units derived fromα-olefin other than propylene in an amount of more than 5% by mol havebeen applied to various uses such as films, heat-sealing layers oflaminated films, and modifiers for improving impact resistance andanti-heat-sealing property of thermoplastic resins, because of theirexcellent transparency, heat-sealing property at low temperature,environmental aging property and impact absorbing capacity. However, theconventional propylene copolymer is not always sufficient intransparency, heat-sealing properties at low temperature, anti-blockingproperties, bleedout resistance, impact strength, etc. for some uses,and the modifiers therefrom are not always sufficient in effect ofimproving heat-sealing property at low temperature and impact strength.Therefore, there has been demanded a propylene copolymer furtherimproved in transparency, environmental aging property and impactstrength, and having excellent in effect of improving heat-sealingproperty at low temperature and impact strength.

In the light of such circumstances as described above, the presentinventors have further studied, and as a result, they have found that apropylene homopolymer obtained by homopolymerization of propylene in thepresence of an olefin polymerization catalyst containing a specifictransition metal compound, and a propylene copolymer obtained bycopolymerization of propylene and at least one kind of α-olefin selectedfrom the group consisting of ethylene and α-olefins having 4 to 20carbon atoms satisfy the above mentioned requisites.

A propylene/ethylene random copolymer containing a small amount ofethylene units is excellent in transparency, rigidity, surface hardness,heat resistance, and hence it is used for films, containers etc.

Heretofore, there is known some methods for preparation of thepropylene/ethylene random copolymer containing a small amount ofethylene units, such as a method using a titanium catalyst systemcomprising a titanium compound and an organoaluminum compound and amethod using a metallocene catalyst system comprising a metallocenecompound (e.g., zirconocene and hafnocene) and an alkylaluminoxane orionic compound.

However, the propylene/ethylene random copolymer obtained by using atitanium catalyst system is not always sufficient in heat-sealingproperty for some uses, and also insufficient in anti-blocking property,bleedout property and impact strength. On the other hand, thepropylene/ethylene random copolymer obtained by using a metallocenecatalyst system is not always sufficient in rigidity, surface hardnessand heat resistance. Therefore, the advent of the propylene/ethylenerandom copolymer having advantages of the both, and excellent in balanceof properties is demanded.

In the light of such circumstances as described above, the presentinventors have further studied, and as a result, they have found that apropylene copolymer containing a specific amount of ethylene unit,having a high triad tacticity, as measured by ¹³ C-NMR, of the propylenechain consisting of head-to-tail bonds, a specific proportion ofinversely inserted propylene units and a specific intrinsic viscosity isexcellent in transparency, rigidity, surface hardness, heat-sealingproperty, anti-blocking property, anti-bleedout property and impactstrength.

Further, the propylene elastomer is excellent in impact absorbingcapacity, heat resistance and heat-sealing property, it is singly usedfor films, and also is used for modifier for thermoplastic resin.

However, when the conventional propylene elastomer is singly used forfilms, the resulting films are not always sufficient in heat-sealingproperty, anti-blocking property and heat resistance. When the elastomeris used for modifier, the effect of improving impact strength is notalways sufficient. Therefore, the advent of the propylene elastomerhaving excellent impact strength, and effective in improving heatresistance, transparency, heat-sealing property, anti-blockingresistance and impact resistance is demanded.

In the light of such circumstances as described above, the presentinventors have further studied, and as a result, they have found that apropylene elastomer containing a specific amount of ethylene unit,having a high triad tacticity, as measured by ¹³ C-NMR, of the propylenechain consisting of head-to-tail bonds, a specific proportion ofinversely inserted propylene units and a specific intrinsic viscosity isexcellent in above mentioned properties, and hence accomplished thepresent invention.

OBJECT OF THE INVENTION

It is an object of the present invention to provide a novel transitionmetal compound useful for an olefin polymerization catalyst componenthaving a high olefin polymerization activity and capable of giving anolefin polymer having high stereoregularity and low in an amount ofinversely inserted units, and to provide an olefin polymerizationcatalyst component comprising said transition metal compound.

It is another object of the invention to provide an olefinpolymerization catalyst containing the above olefin polymerizationcatalyst component and to provide a process for olefin polymerizationusing said olefin polymerization catalyst.

It is a further object of the invention to provide a propylenehomopolymer having excellent rigidity and transparency, a propylenecopolymer having excellent impact strength and transparency, andpropylene elastomer having excellent impact strength and transparency.

SUMMARY OF THE INVENTION

The novel transition metal compound according to the invention is atransition metal compound represented by the following formula (I):##STR5## wherein M is a transition metal of Group IVa, Group Va or GroupVIa of the periodic table;

R¹ is a hydrocarbon group of 2 to 6 carbon atoms;

R² is an aryl group of 6 to 16 carbon atoms, which may be substitutedwith halogen atom, a hydrogen atom, a hydrocarbon group of 1 to 20carbon atoms or an organosilyl group;

X¹ and X² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, an oxygen-containing group or a sulfur-containing group;and

Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, --O--,--CO--, --S--, --SO--, --SO₂ --, --NR³ --, --P(R³)--, --P(O)(R³)--,--BR³ -- or --AlR³ -- (R³ is a hydrogen atom, a halogen atom, ahydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbongroup of 1 to 20 carbon atoms).

The olefin polymerization catalyst component according to the inventioncomprises a transition metal compound represented by the above formula(I).

The first olefin polymerization catalyst according to the inventioncomprises:

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The second olefin polymerization catalyst according to the inventioncomprises:

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

(C) an organoaluminum compound.

The third olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition

metal compound to form an ion pair; said transition metal compound (A)and said at least one compound (B) being supported on the fine particlecarrier.

The fourth olefin polymerization catalyst according to the inventioncomprises:

a solid catalyst component comprising:

a fine particle carrier,

(A) a transition metal compound represented by the above formula (I),and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair,

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier; and

(C) an organoaluminum compound.

The fifth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

a prepolymerized olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair;

(C) an organoaluminum compound; and

a prepolymerized olefin polymer produced by prepolymerization.

The process for olefin polymerization according to the inventioncomprises polymerizing or copolymerizing an olefin in the presence ofany of the first to sixth olefin polymerization catalysts.

The olefin polymerization catalysts according to the invention have highpolymerization activity and an olefin polymer obtained by using thecatalysts has a narrow molecular weight distribution, a narrowcomposition distribution and a large molecular weight. When they areused for polymerizing an α-olefin of 3 or more carbon atoms, obtainableis a polymer having high stereoregularity, low amount of inverselyinserted units, and excellent in heat resistance and rigidity.

The first propylene homopolymer according to the present invention isobtained by polymerizing propylene in the presence of an olefinpolymerization catalyst according to the invention comprising:

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The first propylene copolymer according to the present invention isobtained by copolymerizing propylene and at least one kind of α-olefinselected from the group consisting of ethylene and an α-olefin of 4 to20 carbon atoms in the presence of an olefin polymerization catalystaccording to the invention comprising:

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The propylene homopolymer of the present invention is excellent inrigidity, heat resistance, surface hardness, glossiness, transparencyand impact strength.

The second propylene homopolymer according to the invention has suchproperties that:

(i) a triad tacticity of propylene units chain, as measured by ¹³ C-NMR,is not less than 99.0%;

(ii) a proportion of inversely inserted propylene units based on the2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, is not more than 0.20%; and

(iii) an intrinsic viscosity, as measured in decahydronaphthalene at135° C., is in the range of 0.1 to 20 dl/g.

The propylene polymer of the present invention is excellent in rigidity,heat resistance, surface hardness, glossiness, transparency and impactresistance.

The second propylene copolymer according to the invention has suchproperties that:

(i) said copolymer contains ethylene units in an amount of not more than50% by mol;

(ii) a triad tacticity of propylene units chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 98.0%;

(iii) a proportion of inversely inserted propylene units based on2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, is not more than 0.20%, and

(iv) an intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 20 dl/g.

The propylene copolymer of the present invention (wherein the amount ofmonomer units derived from an α-olefin other than propylene is not morethan 5% by mol) is excellent in transparency, rigidity, surfacehardness, heat resistance, heat-sealing property, anti-blockingproperty, anti-bleedout property and impact strength. The propylenecopolymer of the present invention (wherein the amount of monomer unitsderived from an α-olefin other than propylene is not less than 5% bymol) is excellent in transparency, environmental aging property, andeffective in improving heat-sealing property at low temperature andimpact strength.

The third propylene copolymer according to the invention has suchproperties that:

(i) said copolymer contains propylene units in an amount of 95 to 99.5%by mol and ethylene units in an amount of 0.5 to 5% by mol;

(ii) a triad tacticity of propylene units chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 95.0%;

(iii) a proportion of inversely inserted propylene units based on2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, of 0.05 to 0.5%, and

(iv) an intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 12 dl/g.

The propylene copolymer of the present invention is excellent inrigidity, surface hardness, heat resistance, transparency, heat-sealingproperty, anti-blocking property and anti-bleedout property.

The propylene elastomer according to the invention has such propertiesthat:

(i) said elastomer contains propylene units in an amount of 50 to 95% bymol and ethylene units in an amount of 5 to 50% by mol;

(ii) a triad tacticity of propylene units chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 90.0%;

(iii) a proportion of inversely inserted propylene units based on2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, of 0.05 to 0.5%; and

(iv) an intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 12 dl/g.

The propylene elastomer of the present invention is excellent in heatresistance, impact absorbing capacity, transparency, heat-sealingproperties and anti-blocking properties.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a view illustrating steps of a process for preparing theolefin polymerization catalysts according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

The novel transition metal compound, the olefin polymerization catalystcomponent comprising the transition metal compound, the olefinpolymerization catalyst containing the olefin polymerization catalystcomponent, the process for olefin polymerization using the olefinpolymerization catalyst, the propylene homopolymer, the propylenecopolymer and the propylene elastomer, according to the invention, willbe described in detail hereinafter.

FIG. 1 is a view illustrating steps of a process for preparing theolefin polymerization catalysts according to the invention.

First, the novel transition metal compound according to the invention isdescribed.

The novel transition metal compound of the invention is a transitionmetal compound represented by the following formula (I). ##STR6##

In the formula (I), M is a transition metal of Group IVa, Group Va orGroup VIa of the periodic table. Examples of the transition metalsinclude titanium, zirconium, hafnium, vanadium, niobium, tantalum,chromium, molybdenum and tungsten. Of these, titanium, zirconium andhafnium are preferred, and zirconium is particularly preferred.

R¹ is hydrocarbon group of 2 to 6 carbon atoms. Examples of thehydrocarbon groups of 2 to 6 carbon atoms include an alkyl group such asethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;,n-pentyl, neopentyl and n-hexyl; cycloalkyl group such as cyclohexyl;and an alkenyl group such as vinyl and propenyl.

Of these, preferred is an alkyl group wherein a carbon atom bonding toindenyl group is a primary carbon, more preferred is an alkyl group of 2to 4 carbon atoms, particularly preferred is ethyl group.

R² is an aryl group of 6 to 16 carbon atoms. Examples of the aryl groupof 6 to 16 carbon atoms include phenyl, α-naphthyl, β-naphthyl,anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl,aceanthrenyl, tetrahydronaphthyl, indanyl and biphenylyl. Of these,preferred is phenyl, naphthyl, anthracenyl or phenanthryl.

These aryl groups may be substituted with a halogen atom such asfluorine, chlorine, bromine or iodine;

a hydrocarbon group of 1 to 20 carbon atoms, for example an alkyl groupsuch as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl,dodecyl, icosyl, norbornyl and adamantyl; an alkenyl group such asvinyl, propenyl and cyclohexenyl; arylalkyl group such as benzyl,phenylethyl and phenylpropyl; and an aryl group such as phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthracenyl and phenanthryl; or

an organo-silyl group such as trimethylsilyl, triethylsilyl andtriphenylsilyl.

X¹ and X² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, an oxygen-containing group or a sulfur-containing group.Examples of those atoms and groups include the halogen atoms and thehydrocarbon groups of 1 to 20 carbon atoms as exemplified above.Examples of the halogenated hydrocarbon groups of 1 to 20 carbon atomsinclude the halogenated groups of the above mentioned hydrocarbon groupof 1 to 20 carbon atoms.

Examples of the oxygen-containing groups include a hydroxy group; analkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxygroup such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; andan arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing groups include groups obtained bysubstituting sulfur for oxygen in the above-mentioned oxygen-containinggroups. As the sulfur-containing group, there can be also mentioned asulfonato group such as methylsulfonato, trifluoromethanesulfonato,phenylsulfonato, benzylsulfonato, p-toluenesulfonato,trimethylbenzenesulfonato, triisobutylbenzenesulfonato,p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; and asulfinato group such as methylsulfinato, phenylsulfinato,benzenesulfinato, p-toluenesulfinato, trimethylbenzenesulfinato andpentafluorobenzenesulfinato.

Of these, preferred is halogen atom or hydrocarbon group of 1 to 20carbon atoms.

Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, --O--,--CO--, --S--, --SO--, --SO₂ --, --NR³ --, --P(R³)--, --P(O)(R³)--,--BR³ -- or --AlR³ -- (R³ is a hydrogen atom, a halogen atom, ahydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbongroup of 1 to 20 carbon atoms).

Examples of the divalent hydrocarbon groups of 1 to 20 carbon atomsinclude an alkylene group such as methylene, dimethylmethylene,1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene,1,4-tetramethylene; a cycloalkylene group such as 1,2-cyclohexylene and1,4-cyclohexylene; and an arylalkylene group such as diphenylmethyleneand diphenyl-1,2-ethylene.

Examples of the divalent halogenated hydrocarbon groups include groupsobtained by halogenating the above-mentioned hydrocarbon groups of 1 to20 carbon atoms, such as chloromethylene.

Examples of the divalent silicon-containing groups include analkylsilylene group, an alkylarylsilylene group and an arylsilylenegroup, such as methylsilylene, dimethylsilylene, diethylsilylene,di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene,methylphenylsilylene, diphenylsilylene, di(p-tolyl)silylene anddi(p-chlorophenyl)silylene; and an alkyldisilyl group, analkylaryldisilyl group and an aryldisilyl group, such astetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl.

Examples of the divalent germanium-containing groups include groupsobtained by substituting germanium for silicon in the above-mentioneddivalent silicon-containing groups.

Examples of the atoms and the groups indicated by R³ include the halogenatoms, the hydrocarbon groups of 1 to 20 carbon atoms and thehalogenated hydrocarbon groups of 1 to 20 carbon atoms exemplifiedabove.

Of these, preferred are divalent silicon-containing group and divalentgermanium-containing group, and particularly preferred arealkylsilylene, alkylarylsilylene and arylsilylene.

Listed below are examples of the transition metal compounds representedby the above formula (I).

rac-Dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(o-methylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(m-methylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(p-methylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,5-dimethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,4,6-trimethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(o-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(m-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(p-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,3-dichlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2,6-dichlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(3,5-dichlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(2-bromophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(3-bromophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(4-bromophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(4-biphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-(4-trimethylsilylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis {1-(2-n-propyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(8-methyl-9-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-s-butyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-pentyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-pentyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-butyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(5-acenaphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-i-butyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-neopentyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-neopentyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-hexyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-n-hexyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-methylphenylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride,

rac-methylphenylsilyl-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-methylphenylsilyl-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-methylphenylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-diphenylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-diphenylsilyl-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-diphenylsilyl-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-diphenylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-diphenylsilyl-bis{1-(2-ethyl-4-(4-biphenyl)indenyl)}zirconiumdichloride,

rac-methylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-methylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-ethylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-ethylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,

rac-ethylene-bis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-dimethylgermyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-dimethylgermyl-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconiumdichloride, and

rac-dimethylgermyl-bis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride.

There may also be used the transition metal compounds obtained bysubstituting vanadium metal, niobium metal, tantalum metal, chromiummetal, molybdenum metal or tungsten metal for zirconium metal, titaniummetal or hafnium metal in the above-exemplified compounds.

The transition metal compounds according to the present invention can beprepared in accordance with the methods described in Journal ofOrganometallic Chem. 288 (1985), pages 63 to 67, European PatentPublication No. 0,320,762 specification and Examples thereof, forinstance, by the following manner. ##STR7## wherein, Z represents Cl,Br, I or o-tosyl group, and H₂ R represents ##STR8##

The novel transition metal compound according to the present inventioncan be used as an olefin polymerization catalyst in combination with anorganoaluminum oxy-compound.

The novel transition metal compound is used as an olefin polymerizationcatalyst component in the form of usually a racemic modification, butthe R configuration or the S configuration can be also used.

Next, the olefin polymerization catalyst containing the above-mentionednovel transition metal compound as its catalyst component is described.

The meaning of the term "polymerization" used herein is not limited to"homopolymerization" but may comprehend "copolymerization" Also, themeaning of the term "polymer" used herein is not limited to"homopolymer" but may comprehend "copolymer".

The first and the second olefin polymerization catalysts according tothe invention are described below.

The first olefin polymerization catalyst of the invention is formedfrom:

(A) a transition metal compound represented by the above formula (I)(sometimes referred to as "component (A)" hereinafter); and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The second olefin polymerization catalyst of the invention is formedfrom:

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

(C) an organoaluminum compound.

The organoaluminum oxy-compound (B-1) (hereinafter sometimes referred toas "component (B-1)") used for the first and the second olefinpolymerization catalysts of the invention may be a conventionally knownaluminoxane or may be a benzene-insoluble organoaluminum oxy-compound asdescribed in Japanese Patent Laid-Open Publication No. 78687/1990.

The conventionally known aluminoxane can be prepared, for example, bythe following processes.

(1) A process comprising allowing an organoaluminum compound such astrialkylaluminum to react with a suspension of a compound havingadsorbed water or a salt containing water of crystallization, forexample, hydrate of magnesium chloride, copper sulfane, aluminumsulfate, nickel sulfate or cerous chloride in a hydrocarbon solvent.

(2) A process comprising allowing water, ice or water vapor to directlyreact with an organoaluminum compound such as trialkylaluminum in asolvent such as benzene, toluene, ethyl ether and tetrahydrofuran.

(3) A process comprising allowing an organotin oxide such as dimethyltinoxide and dibutyltin oxide to react with an organoaluminum compound suchas trialkylaluminum in a solvent such as decane, benzene and toluene.

The aluminoxane may contain a small amount of an organometalliccomponent. Moreover, the solvent or the unreacted organoaluminumcompound may be distilled off from the recovered solution of aluminoxanedescribed above, and the resultant product may be dissolved again in asolvent.

Examples of the organoaluminum compounds used for preparing aluminoxaneinclude:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,tripentylaluminum, trihexylaluminum, trioctylaluminum andtridecylaluminum;

tricycloalkylaluminums, such as tricyclohexylaluminum andtricyclooctylaluminum;

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminumchloride;

dialkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride;

dialkylaluminum alkoxides, such as dimethylaluminum methoxide anddiethylaluminum ethoxide; and

dialkylaluminum aryloxides, such as diethylaluminum phenoxide.

Of the organoaluminum compounds, trialkylaluminum andtricycloalkylaluminum are particularly preferred.

Further, there may be also used, as the organoaluminum compound forpreparing aluminoxane, isoprenylaluminum represented by the followingformula (II):

    (i--C.sub.4 H.sub.9).sub.x Al.sub.y (C.sub.5 H.sub.10).sub.z(II)

wherein x, y and z are each a positive number, and z≧2x.

The organoaluminum compounds mentioned above may be used singly or incombination.

Solvents used for preparing aluminoxane include aromatic hydrocarbonssuch as benzene, toluene, xylene, cumene and cymene; aliphatichydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane,hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane,cyclohexane, cyclooctane and methylcyclopentane; petroleum fractionssuch as gasoline, kerosine and gas oil; and halides of theabove-mentioned aromatic, aliphatic and alicyclic hydrocarbons,particularly chlorides and bromides thereof. In addition thereto, etherssuch as ethyl ether and tetrahydrofuran may be also used. Of thesesolvents, particularly preferred are aromatic hydrocarbons.

Examples of the compounds which react with the transition metal compound(A) to form an ion pair (hereinafter sometimes referred to as "component(B-2)"), which are used for the first and the second olefinpolymerization catalysts, include Lewis acid, ionic compounds, boranecompounds and carborane compounds, as described in National Publicationsof international Patent No. 501950/1989 and No. 502036/1989, JapanesePatent Laid-Open Publications No. 179005/1992, No. 179006/1992, No.207703/1992 and No. 207704/1992, and U.S. Pat. No. 547718.

The Lewis acid includes Mg-containing Lewis acid, Al-containing Lewisacid and B-containing Lewis acid. Of these, B-containing Lewis acid ispreferred.

The Lewis acid containing a boron atom (B-containing Lewis acid) is, forexample, a compound represented by the following formula:

    BR.sup.6 R.sup.7 R.sup.8

wherein R⁶, R⁷ and R⁸ are each independently a phenyl group which mayhave a substituent such as a fluorine atom, a methyl group and atrifluoromethyl group, or a fluorine atom.

Examples of the compounds represented by the above formula includetrifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris(3,5-dimethylphenyl)boron. Of these, tris(pentafluorophenyl)boron isparticularly preferred.

The ionic compound used in the invention is a salt comprising a cationiccompound and an anionic compound. An anion reacts with the transitionmetal compound (A) to make the transition metal compound (A) cationicand to form an ion pair so as to stabilize the transition metal cationseed. Examples of such anions include organoboron compound anion andorganoarsenic compound anion, organoaluminum compound anion. Preferredis such anion as is relatively bulky and stabilizes the transition metalcation seed. Examples of cations include metallic cation, organometalliccation, carbonium cation, tripium cation, oxonium cation, sulfoniumcation, phosphonium cation and ammonium cation. More specifically, therecan be mentioned triphenylcarbenium cation, tributylammonium cation,N,N-dimethylammonium cation and ferrocenium cation.

Of these, preferred are ionic compounds containing a boron compound asanion. More specifically, examples of trialkyl-substituted ammoniumsalts include

triethylammoniumtetra(phenyl)boron,

tripropylammoniumtetra(phenyl)boron,

tri(n-butyl)ammoniumtetra(phenyl)boron,

trimethylammoniumtetra(p-tolyl)boron,

trimethylammoniumtetra(o-tolyl)boron,

tributylammoniumtetra(pentafluorophenyl)boron,

tripropylammoniumtetra(o,p-dimethylphenyl)boron,

tributylammoniumtetra(m,m-dimethylphenyl)boron,

tributylammoniumtetra(p-trifluoromethylphenyl)boron,

tri(n-butyl)ammoniumtetra(o-tolyl)boron and

tri(n-butyl)ammoniumtetra(4-fluorophenyl)boron.

Examples of N,N-dialkylanilinium salts include

N,N-dimethylaniliniumtetra(phenyl)boron,

N,N-diethylaniliniumtetra(phenyl)boron and

N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

Examples of dialkylammonium salts include

di(n-propyl)ammoniumtetra(pentafluorophenyl)boron and

dicyclohexylammoniumtetra(phenyl)boron.

Examples of triarylphosphonium salts include

triphenylphosphoniumtetra(phenyl)boron,

tri(methylphenyl)phosphoniumtetra(phenyl)boron and

tri(dimethylphenyl)phosphoniumtetra(phenyl)boron.

Also employable as the ionic compound containing a boron atom are

triphenylcarbeniumtetrakis-(pentafluorophenyl)borate,

N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and

ferroceniumtetrakis(pentafluorophenyl)borate.

Further, the following compounds can be also employed. (In the ioniccompounds enumerated below, the counter ion is tri(n-butyl)ammonium, butthe counter ion is in no way limited thereto.)

That is, there can be mentioned salts of anion, for example,

bis{tri(n-butyl)ammonium}nonaborate,

bis{tri(n-butyl)ammonium}decaborate,

bis{tri(n-butyl)ammonium}undecaborate,

bis{tri(n-butyl)ammonium}dodecaborate,

bis{tri(n-butyl)ammonium)}decachlorodecaborate,

bis{tri(n-butyl)ammonium}dodecachlorododecaborate,

tri(n-butyl)ammonium-1-carbadecaborate,

tri(n-butyl)ammonium-1-carbaundecaborate,

tri(n-butyl)ammonium-1-carbadodecaborate,

tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate and

tri(n-butyl)ammoniumbromo-1-carbadecaborate.

Moreover, borane compounds and carborane compounds can be also employed.These compounds are employed as the Lewis acid or the ionic compounds.

Examples of the borane compounds and the carborane compounds include:

borane and carborane complex compounds and salts of carborane anion, forexample,

decaborane (number of hydrogen=14),

7,8-dicarbaundecaborane(13),

2,7-dicarbaundecaborane(13),

undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,

dodecahydride-11-methyl-2,7-dicarbaundecaborane,

tri(n-butyl)ammonium-6-carbadecaborate(14),

tri(n-butyl)ammonium-6-carbadecaborate(12),

tri(n-butyl)ammonium-7-carbaundecaborate(13),

tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),

tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12),

tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbundecaborate,

tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborateand

tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate; and

carborane and salts of carborane, for example, 4-carbanonaborane(14),1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14),dodecahydride-1-phenyl-1,3-dicarbanonaborane,dodecahydride-1-methyl-1,3-dicarbanonaborane andundecahydride-1,3-dimethyl-1,3-dicarbanonaborane.

Furthermore, the following compounds can be also employed. (In the ioniccompounds enumerated below, the counter ion is tri(n-butyl)ammonium, butthe counter ion is in no way limited thereto.)

That is, there can be mentioned salts of metallic carborane and metallicborane anion, for example,

tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbononaborate)cobaltate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),

tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),

tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),

tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),

tri(n-butyl)ammoniumbis(dodecahydridedicarbadodecaborate)cobaltate(III),

bis{tri(n-butyl)ammonium}bis(dodecahydridedodecaborate)-nickelate(III),

tris{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)chromate(III),

bis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)manganate(IV),

bis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)cobaltate(III)and

bis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)nickelate(IV).

The compounds (B-2) which react with the transition metal compound (A)to form an ion pair can be used in combination of two or more kinds.

The organoaluminum compound (C) (hereinafter sometimes referred to as"component (C)") used for the second olefin polymerization catalyst ofthe invention is, for example, an organoaluminum compound represented bythe following formula (III):

    R.sup.9.sub.n AlX.sub.3-n                                  (III)

wherein R⁹ is a hydrocarbon group of 1 to 12 carbon atoms, X is ahalogen atom or a hydrogen atom, and n is 1 to 3.

In the above formula (III), R⁹ is a hydrocarbon group of 1 to 12 carbonatoms, e.g., an alkyl group, a cycloalkyl group or an aryl group.Particular examples thereof include methyl, ethyl, n-propyl, isopropyl,isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl andtolyl.

Examples of such organoaluminum compounds (C) include:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum, trioctylaluminum andtri(2-ethylhexyl)aluminum;

alkenylaluminums, such as isoprenylaluminum,

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diisopropylaluminum chloride,diisobutylaluminum chloride and dimethylaluminum bromide;

alkylaluminum sesquihalides, such as methylaluminum sesquichloride,ethylaluminum sesquichloride, isopropylaluminum sesquichloride,butylaluminum sesquichloride and ethylaluminum sesquibromide;

alkylaluminum dihalides, such as methylaluminum dichloride,ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminumdibromide; and

alkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride.

Also employable as the organoaluminum compound (C) is a compoundrepresented by the following formula (IV):

    R.sup.9.sub.n AlL.sub.3-n                                  (IV)

wherein R⁹ is the same hydrocarbon as in the above formula (III); L is--OR¹⁰ group, --OSiR¹¹ ₃ group, --OAlR¹² ₂ group, --NR¹³ ₂ group,--SiR¹⁴ ₃ group or --N(R¹⁵)AlR¹⁶ ₂ group; n is 1 to 2; R¹⁰, R¹¹, R¹² andR¹⁶ are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl orthe like; R¹³ is hydrogen, methyl, ethyl, isopropyl, phenyl,trimethylsilyl or the like; and R¹⁴ and R¹⁵ are each methyl, ethyl orthe like.

Examples of such organoaluminum compounds (C) include:

(1) compounds represented by the formula R⁹ _(n) Al(OR¹⁰)_(3-n), forexample, dimethylaluminum methoxide, diethylaluminum ethoxide anddiisobutylaluminum methoxide;

(2) compounds represented by the formula R⁹ _(n) Al(OSiR¹¹ ₃)_(3-n), forexample, Et₂ Al(OSiMe₃), (iso-Bu)₂ Al(OSiMe₃) and (iso-Bu)₂ Al(OSiEt₃);

(3) compounds represented by the formula R⁹ _(n) Al(OAlR¹² ₂)_(3-n), forexample Et₂ AlOAlEt₂ and (iso-Bu)₂ AlOAl(iso-Bu)₂ ;

(4) compounds represented by the formula R⁹ _(n) Al(NR¹³ ₂)_(3-n), forexample, Me₂ AlNEt₂, Et₂ AlNHMe, Method 2 AlNHEt, Et₂ AlN(SiMe₃)₂ and(iso-Bu)₂ AlN(SiMe₃)₂ ;

(5) compounds represented by the formula R⁹ _(n) Al(SiR¹⁴ ₃)_(3-n), forexample, (iso-Bu)₂ AlSiMe₃ ; and

(6) compounds represented by the formula R⁹ _(n) Al(N(R¹⁵)AlR¹⁶₂)_(3-n), for example, Et₂ AlN(Me)AlEt₂ and (iso-Bu)₂AlN(Et)Al(iso-Bu)₂.

Of the organoaluminum compounds represented by the formulas (III) and(IV), the compounds represented by the formulas R⁹ ₃ Al, R⁹ _(n)Al(OR¹⁰)_(3-n) and R⁹ _(n) Al(OAlR¹² ₂)_(3-n) are preferred, and thecompounds having these formulas wherein R is an isoalkyl group and n is2 are particularly preferred.

In the present invention, water may be used as a catalyst component inaddition to the component (A), the component (B-1), the component (B-2)and the component (C). As the water employable in the invention, therecan be mentioned water dissolved in a polymerization solvent describedlater, and adsorbed water or water of crystallization contained in acompound or a salt used for preparing the component (B-1).

The first olefin polymerization catalyst of the invention can beprepared by mixing the component (A) and the component (B-1) (or thecomponent (B-2)), and if desired water (as a catalyst component), in aninert hydrocarbon medium (solvent) or an olefin medium (solvent).

There is no specific limitation on the order of mixing those components,but it is preferred that the component (B-1) (or the component (B-2)) ismixed with water, followed by mixing with the component (A).

The second olefin polymerization catalyst of the invention can beprepared by mixing the component (A), the component (B-1) (or thecomponent (B-2)) and the component (C), and if desired water (as acatalyst component), in an inert hydrocarbon medium (solvent) or anolefin medium (solvent).

There is no specific limitation on the order of mixing those components.However, when the component (B-1) is used, it is preferred that thecomponent (B-1) is mixed with the component (C), followed by mixing withthe component (A). When the component (B-2) is used, it is preferredthat the component (C) is mixed with the component (A), followed bymixing with the component (B-2).

In the mixing of each components, an atomic ratio (Al/transition metal)of aluminum in the component (B-1) to the transition metal in thecomponent (A) is in the range of usually 10 to 10,000, preferably 20 to5,000; and a concentration of the component (A) is in the range of about10⁻⁸ to 10⁻¹ mol/liter-medium, preferably 10⁻⁷ to 5×10⁻²mol/liter-medium.

When the component (B-2) is used, a molar ratio (component (A)/component(B-2)) of the component (A) to the component (B-2) is in the range ofusually 0.01 to 10, preferably 0.1 to 5; and a concentration of thecomponent (A) is in the range of about 10⁻⁸ to 10⁻¹ mol/liter-medium,preferably 10⁻⁷ to 5×10⁻² mol/liter-medium.

In the preparation of the second olefin polymerization catalyst of theinvention, an atomic ratio (Al_(c) /Al_(B-1)) of the aluminum atom(Al_(c)) in the component (C) to the aluminum atom (Al_(B-1)) in thecomponent (B-1) is in the range of usually 0.02 to 20, preferably 0.2 to10.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) is in the range of 0.5 to 50, preferably 1 to 40.

The above-mentioned each components may be mixed in a polymerizer, or amixture of those components beforehand prepared may be fed to apolymerizer.

If the components are beforehand mixed, the mixing temperature is in therange of usually -50° to 150° C., preferably -20° to 120° C.; and thecontact time is in the range of 1 to 1,000 minutes, preferably 5 to 600minutes. The mixing temperature may be varied while the components aremixed and contacted with each other.

Examples of the media (solvents) used for preparing the olefinpolymerization catalyst according to the invention include;

aliphatic hydrocarbons, such as propane, butane, pentane, hexane,heptane, octane, decane, dodecane and kerosine;

alicyclic hydrocarbons, such as cyclopentane, cyclohexane andmethylcyclopentane;

aromatic hydrocarbons, such as benzene, toluene and xylene;

halogenated hydrocarbons, such as ethylene chloride, chlorobenzene anddichcloromethane; and

mixtures of these hydrocarbons.

Next, the third and the fourth olefin polymerization catalysts accordingto the invention are described.

The third olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair;

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier.

The fourth olefin polymerization catalyst according to the inventioncomprises:

a solid catalyst component comprising:

a fine particle carrier,

(A) a transition metal compound represented by the above formula (I),and

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair,

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier; and

(C) an organoaluminum compound.

The transition metal compound (A) used for the third and the fourtholefin polymerization catalysts of the invention is the same as that forthe aforesaid first and second olefin polymerization catalysts, and isrepresented by the above formula (I).

Examples of the organoaluminum oxy-compounds (B-1) used for the thirdand the fourth olefin polymerization catalysts of the invention are thesame as those used for the first and the second olefin polymerizationcatalysts.

Examples of the compounds (B-2) which react with the transition metalcompound (A) to form an ion pair and used for the third and the fourtholefin polymerization catalysts of the invention are the same as thoseused for the first and the second olefin polymerization catalysts.

Examples of the organoaluminum compounds (C) used for the fourth olefinpolymerization catalyst of the invention are the same as those used forthe second olefin polymerization catalyst.

The fine particle carrier used for the third and the fourth olefinpolymerization catalysts of the invention is an inorganic or organiccompound, and is a particulate or granular solid having a particlediameter of 10 to 300 μm, preferably 20 to 200 μm.

The inorganic carrier is preferably porous oxide, and examples thereofinclude SiO₂, Al₂ O₃, MgO, ZrO₂, TiO₂, B₂ O₃, CaO, ZnO, BaO, ThO₂, andmixtures thereof such as SiO₂ --MgO, SiO₂ --Al₂ O₃, SiO₂ --TiO₂, SiO₂--V₂ O₅, SiO₂ --Cr₂ O₃ and SiO₂ --TiO₂ --MgO. Of these, preferred is acarrier containing SiO₂ and/or Al₂ O₃ as its major component.

The above-mentioned inorganic oxides may contain carbonates, sulfates,nitrates and oxides, such as Na₂ CO₃, K₂ CO₃, CaCO₃, MgCO₃, Na₂ SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₂, Na₂ O, K₂ O and Li₂ O, in asmall amount.

The fine particle carrier is varied in its properties depending on thekind and the process for the preparation thereof, but preferably used inthe invention is a carrier having a specific surface area of 50 to 1,000M² /g, preferably 100 to 700 m² /g, and a pore volume of 0.3 to 2.5 cm³/g. The fine particle carrier is used after calcined at 100° to 1,000°C., preferably 150° to 700° C., if necessary.

Also employable as the fine particle carrier in the invention is agranular or particulate solid of an organic compound having a particlediameter of 10 to 300 μm. Examples of the organic compounds include(co)polymers prepared mainly from α-olefins of 2 to 14 carbon atoms suchas ethylene, propylene, 1-butene and 4-methyl-1-pentene, and(co)polymers prepared mainly from vinylcyclohexane or styrene.

The fine particle carrier may contain a surface hydroxyl group or water.In this case, the surface hydroxyl group is contained in an amount ofnot less than 1.0% by weight, preferably 1.5 to 4.0% by weight, morepreferably 2.0 to 3.5% by weight; and water is contained in an amount ofnot less than 1.0% by weight, preferably 1.2 to 20% by weight, morepreferably 1.4 to 15% by weight. The water contained in the fineparticle carrier means water which is adsorbed on the surface of thefine particle carrier.

The amount (% by weight) of the adsorbed water and the amount (% byweight) of the surface hydroxyl group in the fine particle carrier canbe determined in the following manner.

Amount of adsorbed water

The weight reduction of the fine particle carrier after drying at 200°C. under ordinary pressure for 4 hours in a stream of nitrogen ismeasured, and a percentage of the weight after the drying to the weightbefore the drying is calculated.

Amount of surface hydroxyl group

The weight of the fine particle carrier after drying at 200° C. underordinary pressure for 4 hours in a stream of nitrogen is taken as X (g).The carrier is calcined at 1,000° C. for 20 hours to obtain a calcinedproduct containing no surface hydroxyl group. The weight of the calcinedproduct thus obtained is taken as Y (g). The amount (% by weight) of thesurface hydroxyl group is calculated from the following formula. Amount(wt. %) of surface hydroxyl group={(X-Y)/X}×100

Further, in the third and the fourth olefin polymerization catalysts ofthe invention, such water as described in the first and the secondolefin polymerization catalysts may be used as a catalyst component.

The third olefin polymerization catalyst of the invention (i.e., solidcatalyst component) can be prepared by mixing the fine particle carrier,the component (A) and the component (B-1) (or the component (B-2)), andif desired water (catalyst component), in an inert hydrocarbon medium(solvent) or an olefin medium (solvent). In the mixing of thosecomponents, the component (C) can be further added.

There is no specific limitation on the order of mixing those components.

However, preferred processes are:

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2), and then with the component(A), followed by mixing with water if desired;

a process in which a mixture of the component (B-1) (or the component(B-2)) and the component (A) is mixed and contacted with the fineparticle carrier, followed by mixing with water if desired; and

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)) and water, followed bymixing with the component (A).

In the mixing of each components, the component (A) is used in an amountof usually 10⁻⁶ to 5×10⁻³ mol, preferably 3×10⁻⁶ to 10⁻³ mol, per 1 g ofthe fine particle carrier; and a concentration of the component (A) isin the range of about 5×10⁻⁶ to 2×10⁻² mol/liter-medium, preferably2×10⁻⁵ to 10⁻² mol/liter-medium. An atomic ratio (Al/transition metal)of aluminum in the component (B-1) to the transition metal in thecomponent (A) is in the range of usually 10 to 3,000, preferably 20 to2,000. when the component (B-2) is used, a molar ratio (component(A)/component (B-2)) of the component (A) to the component (B-2) is inthe range of usually 0.01 to 10, preferably 0.1 to 5.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) is in the range of 0.5 to 50, preferably 1 to 40.

The temperature for mixing the components is in the range of usually-50° to 150° C., preferably -20° to 120° C.; and the contact time is inthe range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The mixingtemperature may be varied while the components are mixed and contactedwith each other.

The fourth olefin polymerization catalyst according to the invention isformed from the above-mentioned third olefin polymerization catalyst(solid catalyst component) and the organoaluminum compound (C). Thecomponent (C) is used in an amount of not more than 500 mol, preferably5 to 200 mol, per 1 g of the transition metal atom in the component (A)contained in the solid catalyst component.

The third and the fourth olefin polymerization catalysts of theinvention may contain other components useful for the olefinpolymerization than the above-described components.

Examples of the inert hydrocarbon media (solvents) used for preparingthe third and the fourth olefin polymerization catalysts of theinvention are the same as those used for the first and the second olefinpolymerization catalysts.

Next, the fifth and the sixth olefin polymerization catalysts accordingto the invention are described.

The fifth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

a prepolymerized olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair;

(C) an organoaluminum compound; and

a prepolymerized olefin polymer produced by prepolymerization.

Examples of the fine particle carrier used for the fifth and the sixtholefin polymerization catalysts of the invention are the same as thosefor the aforesaid third and fourth olefin polymerization catalysts.

The transition metal compound (A) used for the fifth and the sixtholefin polymerization catalysts of the invention is the same as that forthe aforesaid first and second olefin polymerization catalysts, and isrepresented by the above formula (I).

Examples of the organoaluminum oxy-compounds (B-1) used for the fifthand the sixth olefin polymerization catalysts of the invention are thesame as those used for the first and the second olefin polymerizationcatalysts.

Examples of the compounds (B-2) which react with the transition metalcompound (A) to form an ion pair and used for the fifth and the sixtholefin polymerization catalysts of the invention are the same as thoseused for the first and the second olefin polymerization catalysts.

Examples of the organoaluminum compounds (C) used for the sixth olefinpolymerization catalyst of the invention are the same as those used forthe second olefin polymerization catalyst.

Further, in the fifth and the sixth olefin polymerization catalysts ofthe invention, such water as described in the first and the secondolefin polymerization catalysts may be used as a catalyst component.

The fifth olefin polymerization catalyst of the invention can beprepared by prepolymerizing a small amount of an olefin to the solidcatalyst component. The solid catalyst component is obtained by mixingthe fine particle carrier, the component (A) and the component (B-1) (orthe component (B-2)), and if desired water, in an inert hydrocarbonmedium (solvent) or an olefin medium (solvent). In the mixing of thosecomponents, the component (C) can be further added.

There is no specific limitation on the order of mixing those components.

However, preferred processes are:

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)), and then with thecomponent (A), followed by mixing with water if desired

a process in which a mixture of the component (B-1) (or the component(B-2)) and the component (A) is mixed and contacted with the fineparticle carrier, followed by mixing with water if desired; and

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)) and water, followed bymixing with the component (A).

The mixing of the components is desirably carried out with stirring.

In the mixing of each components, the component (A) is used in an amountof usually 10⁻⁶ to 5×10⁻³ mol, preferably 3×10⁻⁶ to 10⁻³ mol, per 1 g ofthe fine particle carrier; and a concentration of the component (A) isin the range of about 5×10⁻⁶ to 2×10⁻² mol/liter-medium, preferably 10⁻⁵to 10⁻² mol/liter-medium. An atomic weight ratio (Al/transition metal)of aluminum in the component (B-1) to the transition metal in thecomponent (A) is in the range of usually 10 to 3,000, preferably 20 to2,000. When the component (B-2) is used, a molar ratio (component(A)/component (B-2)) of the component (A) to the component (B-2) is inthe range of usually 0.01 to 10, preferably 0.1 to 5.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) is in the range of 0.5 to 50, preferably 1 to 40.

The temperature for mixing the components is in the range of usually-50° to 150° C., preferably -20° to 120° C.; and the contact time is inthe range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The mixingtemperature may be varied while the components are mixed and contactedwith each other.

The fifth olefin polymerization catalyst of the invention can beprepared by prepolymerizing an olefin in the presence of theabove-mentioned components. The prepolymerization can be carried out byintroducing an olefin into an inert hydrocarbon medium (solvent) in the.presence of the components and if necessary the component (c).

In the prepolymerization, the component (A) is used in an amount ofusually 10⁻⁵ to 2×10⁻² mol/liter, preferably 5×10⁻⁵ to 10⁻² mol/liter.The prepolymerization temperature is in the range of -20° to 80° C.,preferably 0° to 50° C.; and the prepolymerization time is 0.5 to 100hours, preferably about 1 to 50 hours.

The olefin used for the prepolymerization is selected from olefins whichare used for polymerization, and it is preferable to use the samemonomer as used in the polymerization or a mixture of the same monomeras used in the polymerization and an α-olefin.

In the olefin polymerization catalyst of the invention obtained asabove, it is desired that the transition metal atom is supported in anamount of about 10⁻⁶ to 10⁻³ g·atom, preferably 2×10⁻⁶ to 3×10⁻⁴ g·atom,per 1 g of the fine particle carrier; and the aluminum atom is supportedin an amount of about 10⁻³ to 10⁻¹ g·atom, preferably 2×10⁻³ to 5×10⁻²g·atom, per 1 g of the fine particle carrier. Further, it is alsodesired that the component (B-2) is supported in an amount of 5×10⁻⁷ to0.1 g·atom, preferably 2×10⁻⁷ to 3×10⁻² g·atom, in terms of the boronatom contained in the component (B-2).

The amount of the prepolymerized polymer prepared by theprepolymerization is desired to be in the range of about 0.1 to 500 g,preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g ofthe fine particle carrier.

The sixth olefin polymerization catalyst of the invention is formed fromthe above-mentioned fifth olefin polymerization catalyst (component) andthe organoaluminum compound (C). The organoaluminum compound (C) is usedin an amount of not more than 500 mol, preferably 5 to 200 mol, per 1g·atom of the transition metal atom in the component (A).

The fifth and the sixth olefin polymerization catalysts of the inventionmay contain other components useful for the olefin polymerization thanthe above-described components.

Examples of the inert hydrocarbon solvents used for the fifth and thesixth olefin polymerization catalysts of the invention are the same asthose used for preparing the aforesaid first and second olefinpolymerization catalysts.

Polyolefins obtained by the use of the olefin polymerization catalystsas described above have a narrow molecular weight distribution, a narrowcomposition distribution and a high molecular weight and the olefinpolymerization catalysts have a high polymerization activity.

Further, when olefins of 3 or more carbon atoms are polymerized in thepresence of the olefin polymerization catalysts, polyolefins havingexcellent stereoregularity can be obtained.

Next, the process for olefin polymerization according to the presentinvention is described.

An olefin is polymerized in the presence of any of the above-describedolefin polymerization catalysts. The polymerization may be carried outby a liquid phase polymerization process such as a suspensionpolymerization or by a gas phase polymerization.

In the liquid phase polymerization process, the same inert hydrocarbonsolvent as used in the preparation of the catalyst can be used, or theolefin itself can be also used as a solvent.

In the polymerization of an olefin using the first or the secondpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g·atom/liter, preferably 10⁻⁷ to 10⁻⁴ g·atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system.

In the polymerization of an olefin using the third or the fourthpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g·atom/liter, preferably 10⁻⁷ to 10⁻⁴ g·atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system. In this case, an aluminoxane which isnot supported on the carrier may be employed, if desired.

In the polymerization of an olefin using the fifth or the sixthpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g·atom/liter, preferably 10⁻⁷ to 10⁻⁴ g·atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system. In this case, an aluminoxane which isnot supported on the carrier may be employed, if desired.

In the slurry polymerization, the temperature for the olefinpolymerization is in the range of usually -100° to 100° C., preferably-50° to 90° C. In the liquid phase polymerization, the temperature is inthe range of usually -100° to 250° C., preferably -50° to 200° C. In thegas phase polymerization process, the temperature is in the range ofusually -47° to 120° C., preferably -40° to 100° C. The polymerizationpressure is in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The polymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the polymerization may be performed in two ormore stages having different reaction conditions.

The molecular weight of the resulting olefin polymer can be regulated byallowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature.

Examples of the olefins to be polymerized using the olefinpolymerization catalysts of the invention include:

α-olefins of 2 to 20 carbon atoms, such as ethylene, propylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene;and

cycloolefins of 3 to 20 carbon atoms, such as cyclopentene,cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Also employable are styrene, vinylcyclohexane, diene, etc.

The olefin polymerization catalyst according to the present invention issuitably used for homopolymerization of propylene or copolymerization ofpropylene with at least one kind of α-olefin selected from the groupconsisting of ethylene and α-olefins of 4 to 20 carbon atoms.

Polyolefin obtained by using the olefin polymerization catalyst of thepresent invention (e.g., said polyolefin is a propylene/ethylenecopolymer containing not less than 50% by mol of propylene unit) usuallyhas a value of Mw/Mn of 1.5 to 3.5, triad tacticity (mm fraction) of notless than 98.0%, a proportion of inversely inserted units based on2,1-insertion of propylene monomer of not more than 0.20%, and aproportion of inversely inserted units based on 1,3-insertion ofpropylene monomer of not more than 0.03%.

When the resulting polyolefin is a propylene homopolymer, said polymerusually has a value of Mw/Mn of 1.5 to 3.5, triad tacticity (mmfraction) of not less than 99.0%, a proportion of inversely insertedunits based on 2,1-insertion of propylene monomer of not more than0.50%, and a proportion of inversely inserted units based on1,3-insertion of propylene monomer of not more than 0.03%.

The propylene homopolymer, the propylene copolymer and the propyleneelastomer according to the invention are described hereinafter.

Propylene homopolymer

The first propylene homopolymer according to the present invention is ahomopolymer of propylene obtained by homopolymerization of propylene inthe presence of the aforementioned catalyst for olefin polymerization.

The propylene homopolymer of the invention desirably has an intrinsicviscosity η!, as measured in decahydronaphthalene at 135° C., of 0.1 to20 dl/g, preferably 0.5 to 10 dl/g, more preferably 1 to 5 dl/g, and avalue of Mw/Mn of 1.5 to 3.5, preferably 2.0 to 3.0, more preferably 2.0to 2.5.

The second propylene homopolymer according to the invention has a triadtacticity of not less than 99.0%, preferably not less than 99.2%, morepreferably not less than 99.5%. The term "triad tacticity" means aproportion of such of three propylene units chains (i.e., chainsconsisting of three propylene units continuously bonded) that thedirections of methyl branches in the propylene chain are the same aseach other and each propylene unit is bonded to each other withhead-to-tail bonds, to total three propylene units chain in the polymer,and this term is sometimes referred to as "mm fraction" hereinafter. Itis also desirably that the proportion of inversely inserted units basedon 2,1-insertion of propylene monomer is in the range of not more than0.50%, preferably not more than 0.18%, more preferably not more than0.15%, and the intrinsic viscosity η!, as measured indecahydronaphthalene at 135° C., is in the range of 0.1 to 20 dl/g,preferably 0.5 to 10 dl/g, more preferably 1 to 5 dl/g,

The propylene homopolymer having a triad tacticity (mm fraction) of notless than 99.0%, a proportion of inversely inserted units based on2,1-insertion of propylene monomer of not more than 0.5%, and anintrinsic viscosity η!, as measured in decahydronaphthalene at 135° C.,of 0.1 to 20 dl/g is novel.

Moreover, in the second propylene homopolymer according to the presentinvention, a proportion of inversely inserted units based on1,3-insertion of propylene monomer is desirably less than the minimumlimit of detection by a measurement of ¹³ C-NMR, and a value of Mw/Mn isdesirably in the range of 1.5 to 3.5, preferably 2.0 to 3.0, morepreferably 2.0 to 2.5.

The second propylene homopolymer of the invention can be prepared byhomopolymerizing propylene in the presence of, for example, theaforesaid olefin polymerization catalysts. The polymerization can becarried out by a liquid phase polymerization (e.g., a suspensionpolymerization and a solution polymerization) or a gas phasepolymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, or propylenecan be also used as a solvent.

In the suspension polymerization, the temperature for polymerizingpropylene is in the range of usually -50° to 100° C., preferably 0° to90° C. In the solution polymerization, the temperature is in the rangeof usually 0° to 250° C., preferably 20° to 200° C. In the gas phasepolymerization, the temperature is in the range of usually 0° to 120°C., preferably 20° to 100° C. The polymerization pressure is in therange of usually atmospheric pressure to 100 kg/cm², preferablyatmospheric pressure to 50 kg/cm². The polymerization reaction can becarried out either batchwise, semicontinuously or continuously. Further,the polymerization can be carried out in two or more stages havingdifferent reaction conditions.

The molecular weight of the resultant propylene polymer can be regulatedby allowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature and the polymerization pressure.

Propylene copolymer

The first propylene copolymer according to the present invention is apropylene/α-olefin copolymer obtained by copolymerization of propyleneand at least one kind of α-olefin selected from the group consisting ofethylene and a-olefins of 4 to 20 carbon atoms in the presence of theaforementioned catalyst for olefin polymerization.

The propylene copolymer contains propylene units in an amount of notless than 50% by mol, preferably not less than 60% by mol, morepreferably not less than 70% by mol, and comonomer units derived fromthe α-olefin selected from the group consisting of ethylene andα-olefins of 4 to 20 carbon atoms in an amount of not more than 50% bymol, preferably 5 to 40% by mol, more preferably 10 to 30% by mol.

Examples of α-olefin of 4 to 20 carbon atoms include 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene,2-ethyl-1-hexene, 1-decene, 1-dodecene, 1-tetradecene and 1-eicosene.

Of these, preferred comonomers used for copolymerization includeethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.

In the present invention, composition of the propylene copolymer isdetermined by using ¹³ C-NMR.

The propylene copolymer has an intrinsic viscosity η!, as measured indecahydronaphthalene at 135° C., of 0.1 to 20 dl/g, preferably 0.5 to 10dl/g, more preferably 1 to 5 dl/g, and a value of Mw/Mn of 1.5 to 3.5,preferably 2.0 to 3.0, more preferably 2.0 to 2.5.

The second propylene copolymer according to the present inventioncontains propylene units in an amount of not less than 50% by mol,preferably not less than 60% by mol, more preferably not less than 70%by tool, and ethylene units in an amount of not more than 50% by mol,preferably 5 to 40% by mol, more preferably 10 to 30% by mol. Thepropylene copolymer may contain constituent units derived from otherolefins than propylene and ethylene, for example, monomer units derivedfrom other monomers such as the aforementioned α-olefins of 4 to 20carbon atoms and dienes in a small amount.

The second propylene copolymer according to the invention has a triadtacticity (mm fraction) of not less than 98.0%, preferably not less than98.2%, more preferably not less than 98.5%. It is also desirably thatthe proportion of inversely inserted units based on 2,1-insertion ofpropylene monomer is in the range of not more than 0.50%, preferably notmore than 0.18%, more preferably not more than 0.15%, and an intrinsicviscosity η!, as measured in decahydronaphthalene at 135° C., is in therange of 0.1 to 20 dl/g, preferably 0.5 to 10 dl/g, more preferably 1 to5 dl/g.

The propylene/ethylene random copolymer having a triad tacticity (mmfraction) of not less than 98.0%, a proportion of inversely insertedunits based on 2,1-insertion of propylene monomer of not more than 0.5%,and an intrinsic viscosity η!, as measured in decahydronaphthalene at135° C., of 0.1 to 20 dl/g is novel.

Moreover, in the second propylene copolymer according to the presentinvention, a proportion of inversely inserted units based on1,3-insertion of propylene monomer is desirably less than the minimumlimit of detection by a measurement of ¹³ C-NMR, and a value of Mw/Mn isdesirably in the range of 1.5 to 3.5, preferably 2.0 to 3.0, morepreferably 2.0 to 2.5.

The second propylene copolymer of the invention can be prepared bycopolymerizing propylene and ethylene in the presence of, for example,the aforesaid olefin polymerization catalysts. The copolymerization canbe carried out by a liquid phase polymerization (e.g., a suspensionpolymerization and a solution polymerization) or a gas phasepolymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, or propyleneand/or ethylene can be also used as a solvent.

In the suspension polymerization, the temperature for copolymerizingpropylene and ethylene is in the range of usually -50° to 100° C.,preferably 0° to 90° C. In the solution polymerization, the temperatureis in the range of usually 0° to 250° C., preferably 20° to 200° C. Inthe gas phase polymerization, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The copolymerization pressureis in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The copolymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the copolymerization can be carried out in two ormore stages having different reaction conditions.

The third propylene copolymer according to the present inventioncontains propylene units in an amount of 95 to 99.5% by mol, preferably95 to 99% by mol, more preferably 95 to 98% by mol, and ethylene unitsin an amount of 0.5 to 5% by mol, preferably 1 to 5% by mol, morepreferably 2 to 5% by mol.

The propylene copolymer may contain constituent units derived from otherolefins than propylene and ethylene in an amount of not more than 5% bymol.

The third propylene copolymer according to the invention has a triadtacticity of not less than 95.0%, preferably not less than 96.0%, morepreferably not less than 97.0%. It is also desirably that the proportionof inversely inserted units based on 2,1-insertion of propylene monomeris in the range of 0.05 to 0.5%, preferably 0.05 to 0.4%, morepreferably 0.05 to 0.3%, and the intrinsic viscosity η!, as measured indecahydronaphthalene at 135° C., is in the range of 0.1 to 12 dl/g,preferably 0.5 to 12 dl/g, more preferably 1 to 12 dl/g,

In the propylene copolymer of the invention, thea proportion ofinversely inserted units based on 1,3-insertion of propylene monomer isdesirably not more than 0.05%.

The third propylene copolymer according to the present invention can beprepared by copolymerizing ethylene and propylene in the presence of anolefin polymerization catalyst, for example, a catalyst comprising:

(A) a transition metal compound represented by the following formula(Ia);

(B) at least one compound selected from the group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and optionally,

(C) an organoaluminum compound.

The transition metal compound used in the preparation of the thirdpropylene copolymer according to the present invention is a transitionmetal compound represented by the following formula (Ia). ##STR9##

In the formula (Ia), M is a transition metal atom mentioned in theaforementioned formula (I).

R^(a) is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, asilicon-containing group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group or aphosphorus-containing group. Examples of the halogen atoms, thehydrocarbon groups of 1 to 20 carbon atoms, the halogenated hydrocarbongroups of 1 to 20 carbon atoms include the atoms and groups exemplifiedfor X¹ and X² in the aforementioned formula (I).

Examples of the silicon-containing groups includemonohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl;dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;trihydrocarbon-substituted silyl such as trimethylsilyl, triethylsilyl,tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl,methyldiphenylsilyl, tritolylsityl and trinaphthylsilyl; silyl ether ofhydrocarbon-substituted silyl such as trimethylsilyl ether;silicon-substituted alkyl group such as trimethylsilylmethyl; andsilicon-substituted aryl group such as trimethylphenyl.

Examples of the oxygen-containing groups include a hydroxy group; analkoxy group such as methoxy, ethoxy, propoxy and butoxy; an allyloxygroup such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; andan arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing groups include groups obtained bysubstituting sulfur for oxygen in the above-mentioned oxygen-containinggroups.

Examples of the nitrogen-containing groups include an amino group; analkylamino group such as methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino and dicyclohexylamino; an arylamino groupsuch as phenylamino, diphenylamino, ditolylamino, dinaphthylamino andmethylphenylamino; and an alkylarylamino group.

Examples of the phosphorus-containing groups include a phosphino groupsuch as dimethylphosphino and diphenylphosphino.

Of these, R^(a) is preferably a hydrocarbon group, particularly ahydrocarbon group of 1 to 4 carbon atoms such as methyl, ethyl, propyland butyl.

R^(b) is aryl group of 6 to 16 carbon atoms, and examples thereof arethe same as the groups described as R².

The aryl groups may be substituted with a halogen atom, a hydrocarbongroup of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to20 carbon atoms, as same as the afrementioned R^(a).

X¹ and X² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, an oxygen-containing group or a sulfur-containing group.Examples of those atoms and groups include the halogen atoms, thehydrocarbon groups of 1 to 20 carbon atoms, the halogenated hydrocarbongroups of 1 to 20 carbon atoms and the oxygen-containing groupsexemplified above with respect to X¹ and X² as described in theaforementioned formula (I).

Y¹ is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, adivalent tin-containing group, --O--, --CO--, --S--, --SO--, --SO₂ --,--NR³ --, --P(R³)--, --P(O)(R³)--, --BR³ -- or --AlR³ -- (R³ is ahydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms).Examples thereof include the same groups mentioned as Y in theaforementioned formula (I) and divalent tin-containing groups includegroups obtained by substituting tin for silicon in the above-mentioneddivalent silicon-containing groups.

Of these, preferred are a divalent silicon-containing group, a divalentgermanium-containing group and a divalent tin-containing group. Morepreferred is a divalent silicon-containing group. Of thesilicon-containing groups, alkylsilylene, alkylarylsilylene andarylsilylene are particularly preferred.

Listed below are examples of the transition metal compounds representedby the above formula (Ia).

rac-Dimethylsilyl-bis{1-(4-phenylindenyl)}zirconium dichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(α-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(β-naphthyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(1-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(2-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(9-anthracenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-fluorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(pentafluorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(m-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(o-chlorophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(o,p-dichlorophenyl)phenyl-1-indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-bromophenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-tolyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(m-tolyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(o-tolyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(o,o'-dimethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-ethylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-i-propylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-benzylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-biphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(m-biphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(p-trimethylsilylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-(m-trimethylsilylphenyl)indenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-Diphenylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,

rac-Dimethylsilyl-bis{1-(2-phenyl-4-phenylindenyl)}zirconium dichloride,

rac-Dimethylsilyl-bis{1-(2-n-propyl-4-phenylindenyl)}zirconiumdichloride,

rac-Diethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,

rac-Di-(i-propyl)silyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,

rac-Di-(n-butyl)silyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,

rac-Dicyclohexylsilyl-bis{1-(2-methyl-4-phenylindenyl}zirconiumdichloride,

rac-methylphenylsilyl-bis{1-(2-methyl-4-phenylindenyl}zirconiumdichloride,

rac-diphenylsilyl-bis{1-(2-methyl-4-phenylindenyl}zirconium dichloride,

rac-di(p-tolyl)silyl-bis{1-(2-methyl-4-phenylindenyl}zirconiumdichloride,

rac-di(p-chlorophenyl)silyl-bis{1-(2-methyl-4-phenylindenyl}zirconiumdichloride,

rac-methylene-bis{1-(2-methyl-4-phenylindenyl}zirconium dichloride,

rac-ethylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,

rac-dimethylgermyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdichloride,

rac-dimethylstanyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dibromide,

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dimethyl,

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiummethylchloride,

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride, mono(trifluoromethanesulfonato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoromethanesulfonato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(p-toluenesulfonato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(methylsulfonato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoromethanesulfinato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(trifluoroacetato),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride(n-butoxide),

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiumdi(n-butoxide), and

rac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconiummonochloride(phenoxide).

There may also be used the transition metal compounds obtained bysubstituting titanium metal, hafnium metal, vanadium metal, niobiummetal, tantalum metal, chromium metal, molybdenum metal or tungstenmetal for zirconium metal in the above-exemplified compounds.

The transition metal compound is used as an olefin polymerizationcatalyst component in the form of usually a racemic modification, butthe R configuration or the S configuration can be also used.

An olefin polymerization catalyst used for the preparation of thepropylene copolymer according to the present invention is a catalystobtained by replacing the component (A) of the first to sixth olefinpolymerization catalysts with the transition metal compound representedby the aforementioned formula (Ia).

The propylene copolymer of the invention can be prepared bycopolymerizing propylene and ethylene in the presence of, for example,the aforesaid olefin polymerization catalysts. The copolymerization canbe carried out by a liquid phase polymerization (e.g., a suspensionpolymerization and a solution polymerization) or a gas phasepolymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, and propyleneand/or ethylene can be also used as a solvent.

In the suspension polymerization, the temperature for copolymerizingpropylene and ethylene is in the range of usually -50° to 100° C.,preferably 0° to 90° C. In the solution polymerization, the temperatureis in the range of usually 0° to 250° C., preferably 20° to 200° C. Inthe gas phase polymerization, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The copolymerization pressureis in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The copolymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the copolymerization can be carried out in two ormore stages having different reaction conditions.

The molecular weight of the resultant propylene copolymer can beregulated by allowing hydrogen to exist in the copolymerization systemor by varying the copolymerization temperature and the copolymerizationpressure.

Propylene elastomer

The propylene elastomer of the invention is a propylene/ethylene randomcopolymer containing propylene units in an amount of 50 to 95% by mol,preferably 60 to 93% by mol, more preferably 70 to 90% by mol, andcontaining ethylene units in an amount of 5 to 50% by mol, preferably 7to 40% by mol, more preferably 10 to 30% by mol.

The propylene elastomer may contain constituent units derived from otherolefins than propylene and ethylene in an amount of not more than 10% bymol.

In the propylene elastomer of the invention, it is desirably that thetriad tacticity is not less than 90.0%, preferably not less than 93.0%,more preferably not less than 96.0%, a proportion of inversely insertedunits based on 2,1-insertion of propylene monomer is 0.05 to 0.5%,preferably 0.05 to 0.4%, more preferably 0.05 to 0.3%, and an intrinsicviscosity η!, as measured in decahydronaphthalene at 135° C., is 0.1 to12 dl/g, preferably 0.5 to 12 dl/g, more preferably 1 to 12 dl/g.

Moreover, in the propylene elastomer according to the present invention,a proportion of inversely inserted units based on 1,3-insertion ofpropylene monomer is desirably not more than 0.05%, preferably not morethan 0.03.

The propylene elastomer of the invention can be prepared bycopolymerizing propylene and ethylene in the presence of, for example,the aforesaid olefin polymerization catalyst used in the preparation ofthe third propylene copolymer. The copolymerization can be carried outby a liquid phase polymerization (e.g., a suspension polymerization anda solution polymerization) or a gas phase polymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, and propyleneand/or ethylene can be also used as a solvent.

In the suspension polymerization, the temperature for copolymerizingpropylene and ethylene is in the range of usually -50 to 100° C.,preferably 0° to 90° C. In the solution polymerization, the temperatureis in the range of usually 0° to 250° C., preferably 20° to 200° C. Inthe gas phase polymerization, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The copolymerization pressureis in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The copolymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the copolymerization can be carried out in two ormore stages having different reaction conditions.

The molecular weight of the resultant propylene copolymer can beregulated by allowing hydrogen to exist in the copolymerization systemor by varying the copolymerization temperature and the copolymerizationpressure.

In the present invention, the molecular weight distribution (Mw/Mn), thetriad tacticity (mm fraction), the proportion of inversely insertedunits based on 2,1-insertion of propylene monomer, and the proportion ofinversely inserted units based on 1,3-insertion of propylene monomer aredetermined by the following manner.

Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was determined from a chromatograph measured using Gelpermeation chromatography (GPC) (150-ALC/GPC™, manufactured by WatersCo.). The measurement was conducted at temperature of 140° C. by usingcolumn of GMH-HT and GMH-HLT type (both manufactured by Toyo Soda K.K),and o-dichlorobenzene as an eluting solvent. From the chromatograph, anumber average molecular weight (Mn) and a weight average molecularweight (Mw), both in terms of polypropylene by universal method (withthe proviso that when the comonomer content is not less than 10% by mol,polystyrene standard was used) were calculated to obtain Mw/Mn.

Triad Tacticity (mm fraction)

Triad tacticity (mm fraction) of the propylene copolymer is determinedby defining as a proportion of such chains of three propylene units thatdirections of methyl branches in the propylene chain are the same aseach other and each propylene units bonded to each other withhead-to-tail bonds, when the main chains are represented by plane-zigzagstructure. The triad tacticity (mm fraction) of the propylene copolymercan be determined from a ¹³ C-NMR spectrum of the propylene copolymerand the following formula: ##EQU1## wherein PPP(mm), PPP(mr) and PPP(rr)denote peak areas derived from the methyl groups of the second units inthe following three propylene units chain consisting of head-to-tailbonds, respectively: ##STR10##

The ¹³ H-NMR spectrum is measured in the following manner. A sample iscompletely dissolved in a mixed solvent containing about 0.5 ml ofhexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene andabout 0.05 ml of deuterated benzene (i.e., lock solvent) in an NMRsample tube (diameter: 5 mm), and then subjected to a proton perfectdecoupling method at 120° C. to measure the ¹³ H-NMR spectrum. Themeasurement is conducted under the conditions of a flip angle of 45° anda pulse interval of not less than 3.4 T₁ (T₁ is a maximum value withrespect to a spin-lattice relaxation time of the methyl group). In thepolypropylene, T₁ of the methylene group and T₁ of the methine group areeach shorter than that of the methyl group, and hence the magnetizationrecovery of all carbons under these conditions is not less than 99%.With respect to the chemical shift, the methyl group of the third unitin the five propylene units chain consisting of head-to-tail bonds isset to 21.593 ppm, and the chemical shift of other carbon peak isdetermined by using the above-mentioned value as a reference.

The spectrum is classified into the first region (21.1-21.9 ppm), thesecond region (20.3-21.0 ppm) and the third region (19.5-20.3 ppm).

In the first region, the methyl group of the second unit in the threepropylene units chain represented by PPP(mm) resonates.

In the second region, the methyl group of the second unit in the threepropylene units chain represented by PPP(mr) resonates and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonate.

In the third region, the methyl group of the second unit in the threepropylene units chain represented by PPP(rr) resonates and the methylgroup (EPE-methyl group) of a propylene unit whose adjacent units areethylene units resonate.

Further, the propylene copolymer has the following structures (i), (ii)and (iii) containing an inversely inserted unit. ##STR11##

Among the peaks derived from the structures (i), (ii) and (iii), peaksof the carbon A and the carbon B do not appear in the first to thirdregions, because the carbon A resonates at 17.3 ppm and the carbon Bresonates at 17.0 ppm. Further, the carbon A and the carbon B do notrelate to the three propylene units chain, and hence it is not necessaryto take these carbons into consideration of calculation of triadtacticity.

Peaks of the carbon C, carbon D and carbon D' appear in the secondregion; and peaks of the carbon E and carbon E' appear in the thirdregion.

Of the peaks in the first to third regions as described above, peakswhich are not based on the three propylene units chain consisting ofhead-to-tail bonds are peaks based on the PPE-methyl group (resonance inthe vicinity of 20.7 ppm), the EPE-methyl group (resonance in thevicinity of 19.8 ppm), the carbon C, the carbon D, the carbon D', thecarbon E and the carbon E'.

The peak area based on the PPE-methyl group can be evaluated by the peakarea of the PPE-methine group (resonance in the vicinity of 30.6 ppm),and the peak area based on the EPE-methyl group can be evaluated by thepeak area of the EPE-methine group (resonance in the vicinity of 32.9ppm). The peak area based on the carbon C can be evaluated by the peakarea of the adjacent methine group (resonance in the vicinity of 31.3ppm), the peak area based on the carbon D can be evaluated by 1/2 asmuch as the sum of the peak areas of the αβ methylene carbons of thestructure (ii) (resonance in the vicinity of 34.3 ppm and resonance inthe vicinity of 34.5 ppm, respectively), and the peak area based on thecarbon D' can be evaluated by the peak area of the adjacent methinegroup of the methyl group of the carbon E' of the aforementionedstructure (iii) (resonance in the vicinity of 33.3 ppm), the peak areabased on the carbon E can be evaluated by the peak area of the adjacentmethine group (resonance in the vicinity of 33.7 ppm) and the peak areabased on the carbon E' can be evaluated by the peak area of the adjacentmethine group (resonance in the vicinity of 33.3 ppm).

Accordingly, by subtracting these peak areas from the total peak areasof the second region and the third region, the peak areas based on thethree propylene units chain (PPP(mr) and PPP(rr)) consisting ofhead-to-tail bonds can be obtained.

Thus, the peak areas of PPP(mm), PPP(mr) and PPP(rr) can be evaluated,and hence the triad tacticity of the propylene units chain consisting ofhead-to tail bonds can be determined.

Triad tacticity (mm fraction) of the propylene homopolymer is alsodetermined by defining as a proportion of such chains of three propyleneunits that directions of methyl branches in the propylene chain are thesame as each other and each propylene units bonded to each other withhead-to-tail bonds, when the main chains are represented by plane-zigzagstructure. The triad tacticity (mm fraction) of the propylenehomopolymer can be determined from a ¹³ C-NMR spectrum of the propylenecopolymer and the following formula: ##EQU2## wherein PPP(mm) has thesame meanings defined above, and ΣICH₃ denotes the total areas of allpeaks derived from the methyl groups.

With respect to the chemical shift, the methyl group of the third unitin the five propylene units chain consisting of head-to-tail bonds isset to 21.593 ppm, and the chemical shift of other carbon peak isdetermined by using the above-mentioned value as a reference.

In this standard, the peak of the methyl group of the second unit in thethree propylene units chain represented by PPP(mm) appears in the rangeof 21.1 to 21.9 ppm, the peak of the methyl group of the second unit inthe three propylene units chain represented by PPP(mr) appears in therange of 20.3 to 21.0 ppm and the peak of the methyl group of the secondunit in the three propylene units chain represented by PPP(rr) appearsin the range of 19.5 to 20.3 ppm.

Here, the propylene homopolymer contains a small amount of partialstructure comprising inversely inserted units based on the 2,1-insertionrepresented by the aforementioned structure (i), in addition to theregular structure consisting of head-to-tail bonds of propylene units.

In the irregular structure represented by the aforementioned structure(i), the aforementioned definition of PPP(mm) is not applied to thecarbon A, the carbon B and the carbon C. However, the carbon A and thecarbon B resonate in the region of 16.5 to 17.5 ppm, and the carbon Cresonates in the vicinity of 20.7 ppm (PPP(mr) region). In the partialstructure containing inversely inserted units, not only the peak of themethyl group but also the peaks of the adjacent methylene and methinegroup must be confirmed. Therefore, the carbon A, the carbon B and thecarbon C are not included in the region of PPP(mm).

Thus, the triad tacticity (mm fraction) of the propylene homopolymer canbe calculated from the aforementioned formula.

Proportion of inversely inserted units based on 2,1-insertion ofpropylene monomer

In the polymerization, the 1,2-insertion (methylene side is bonded tothe catalyst) of the propylene monomer mainly takes place, but the2,1-insertion insertion thereof sometimes takes place. Therefore, thepropylene copolymer and the propylene elastomer contain the inverselyinserted units based on the 2,1-insertion represented by theaforementioned structures (i), (ii) and (iii). The proportion of theinversely inserted units based on the 2,1-insertion was calculated fromthe following formula by using ¹³ H-NMR. ##EQU3##

Naming of these peaks was made in accordance with the method by Carman,et al. (Rubber Chem. Tachnol., 44, 781 (1971)). Iαβ and the likeindicate the peak areas of αβ-peak and the like.

Homopolymer of propylene contains the inversely inverted units based onthe 2,1-insertion. The proportion of the 2,1-propylene monomerinsertions to the all propylene insertions was calculated from thefollowing formula. ##EQU4## wherein, ΣI_(CH).sbsb.3 is the same as thosementioned before. Proportion of inversely inserted units based on1,3-insertion of propylene monomer

In the propylene copolymer and the propylene elastomer, the amount ofthree units chain based on the 1,3-insertion of propylene is determinedfrom βγ-peak (resonance in the vicinity of 27.4 ppm).

In the propylene homopolymer, the amount of 3 unit chain based on the1,3-insertion of propylene is determined from αδ-peak (resonance in thevicinity of 37.1 ppm) and βγ-peak (resonance in the vicinity of 27.4ppm).

EFFECT OF THE INVENTION

The novel transition metal compound according to the invention cansuitably be used as an olefin polymerization catalyst component.

The olefin polymerization catalyst of the invention has highpolymerization activity and polyolefins prepared by the use of thecatalyst have a narrow molecular weight distribution, a narrowcomposition distribution and high molecular weight. When an α-olefin of3 or more carbon atoms is used, obtainable is a polymer having highstereoregularity, being low in proportion of inversely inserted units,and having excellent in heat resistance and rigidity.

The propylene homopolymer according to the present invention isexcellent in rigidity, heat resistance, surface hardness, glossiness,transparency and impact strength.

The first-and second propylene copolymers of the present invention(wherein the amount of monomer units derived from an α-olefin other thanpropylene is not more than 5% by mol) are excellent in transparency,rigidity, surface hardness, heat resistance, heat-sealing property,anti-blocking property, anti-bleedout property and impact strength. Thepropylene copolymers of the present invention (wherein the amount ofmonomer units derived from an α-olefin other than propylene is not lessthan 5% by mol) are excellent in transparency, environmental agingproperty, and effective in improving heat-sealing property at lowtemperature and impact strength.

The third propylene copolymer according to the invention is excellent inrigidity, surface hardness, heat resistance, transparency, heat-sealingproperty, anti-blocking property and anti-bleedout property, andsuitable for films, sheets, containers, stretched yarns, nonwovenfabrics, etc.

The propylene elastomer according the invention is excellent in heatresistance, impact absorbing properties, transparency, heat-sealingproperties and anti-blocking properties. Hence, it can be singly usedfor films, sheets, etc., and moreover it can be suitably used as amodifier of a thermoplastic resin.

EXAMPLE

The present invention is described in more detail with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

In the present invention, an intrinsic viscosity η! and the compositionof a copolymer are determined by the following methods.

Further, in some examples, a heat seal-starting temperature and a heatseal-starting temperature after heat treatment, a melting point (Tm), amelt flow rate (MFR), an izod impact strength (IZ) and a film impactstrength are measured by the following method.

Intrinsic viscosity η!

The intrinsic viscosity η! was determined in decahydronaphthalene at135° C., and expressed by dl/g.

Composition of copolymer

The composition of a propylene copolymer is measured by ¹³ H-NMR.

Heat seal-starting temperature and heat seal-starting temperature afterheat treatment

With respect to the T-die film having a width of 30 cm and a thicknessof 50 μm prepared using a single screw extruder having a diameter of 30mm under the conditions of a resin temperature of 210° C. (at a portionof dicer of extruder), a take-off speed of 3 m/min and a temperature ofcooling roll of 25° C., a heat seal of two films is carried out using aheat sealer by sealing at various seal bar temperatures under theconditions of a heat seal pressure of 2 kg/cm², a seal time of 1 secondand a width of 5 mm to prepare a sealed film having a width of 15 mm.The above-prepared sealed film was allowed to stand overnight.

The heat seal-staring temperature is defined as a temperature of theheat sealer when the peeling resistance of the sealed film becomes 300g/25 mm, under such conditions that the sealed film is peeled off at 23°C., a peeling speed of 200 mm/min and a peeling angle of 180°.

Separately, another sealed film was subjected to heat treatment at 50°C. for 7 days. The heat seal-starting temperature after heat treatmentwas measured using the heat treated specimen.

Melting point (Tm)

The melting point was determined from an endothermic curve given byheating about 5 mg of a sample charged in an aluminum pan to 200° C. ata rate of 10° C./min, keeping it at 200° C. for 5 minutes, then coolingit to room temperature at a rate of 20° C./min and heating it again at arate of 10° C./min. The measurement was conducted using a DSC-7 typeapparatus produced by Perkin Elmer Co.

Melt flow rate (MFR)

The MFR is measured in accordance with ASTM D 1238 under a load of 2.16kg at 230°

Izod impact strength (IZ)

The IZ is measured in accordance with ASTM D 256 at 23° C. using anotched specimen of 12.7 mm (width)×6.4 mm (thickness)×64 mm (length).

The specimen is prepared by injection molding at a resin temperature of200° C. and a molding temperature of 40° C. using a polypropylenecomposition obtained by dry-blending 20% by weight of a polymeraccording to the present invention and 80% by weight of a polypropylene(HIPOL™, grade J 700, melt flow rate: 11 g/10 min (at 230° C.), density:0.91, manufactured by Mitsui Petrochemical industries, Ltd.), andmelt-kneading at 200° C. using a twin-screw extruder.

Film impact strength

The film impact strength is measured using a film impact tester(manufactured by Toyo Seiki K. K., diameter of impact head bulb: 1/2inch (12.7 mm φ)).

Example 1 Synthesis ofrac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideSynthesis of 3-(2-biphenylyl)-2-ethylpropionic acid

A 500-ml four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 13.46 g(120 mmol) of potassium t-butoxide, 100 ml of toluene and 20 ml ofN-methylpyrrolidone. To the mixture was dropwise added a solutioncontaining 20.7 g (110 mmol) of diethyl ethylmalonate dissolved in 50 mlof toluene under nitrogen atmosphere while warming at 60° C. After theaddition was completed, the reaction mixture was stirred for 1 hour atthis temperature. Then, to the resulting mixture was dropwise added asolution containing 20.27 g (100 mmol) of 2-phenylbenzylbromidedissolved in 30 ml of toluene. After the addition was completed, thetemperature was elevated and the resulting mixture was stirred underreflux for 2 hours. The reaction mixture was poured onto 200 ml of waterand the resulting mixture was adjusted with addition of 2N HCl to pH 1.The organic phase was separated and the aqueous phase was furtherextracted with 100 ml of toluene three times. The combined organic phasewas washed with a saturated aqueous solution of sodium chloride untilthe resulting material was neutralized, followed by drying overanhydrous Na₂ SO₄. The solvent was concentrated under reduced pressureto obtain 36.7 g of a yellow-orange liquid.

A 1-liter four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 67.3 g(1.02 mol) of potassium hydoxide and 160 ml of an aqueous solution ofmethanol (methanol/water=4/1(v/v)). To the mixture was dropwise added asolution containing the above-obtained concentrate dissolved in 50 ml ofan aqueous solution of methanol (methanol/water=4/1(v/v)) at roomtemperature under a nitrogen atmosphere. After the addition wascompleted, the temperature was elevated and the resulting mixture wasstirred under reflux for 4 hours. Thereafter, the temperature was cooledto room temperature and the resultant precipitated solid was filtered.The residue was dissolved in water and acidified with addition ofsulfuric acid to pH 1. The resulting solution was extracted with 100 mlof methylene chloride five times. The combined organic phase was driedover anhydrous Na₂ SO₄. The solvent was concentrated under reducedpressure to obtain 24.2 g of a white solid.

Then, a 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a thermometer was charged with 24.2 g of theabove-obtained white solid, 56 ml of acetic acid, 37 ml of water and13.1 ml of concentrated sulfuric acid, and the mixture was stirred underreflux for 6 hours under a nitrogen atmosphere. After the reaction wascompleted, the acetic acid was evaporated under reduced pressure. To theresulting material was added 50 ml of water, which was then extractedwith 50 ml of methylene chloride three times. The combined organic phasewas washed with 50 ml of a saturated aqueous solution of sodiumchloride, followed by drying over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure. The residue was chromatographed onsilica gel (eluting with hexane/ethyl acetate (2/1), and hexane/ethylacetate (1/1), parts by volume) to obtain 13.7 g of the desired productas a white solid (yield: 54%).

FD-MS: 254 (M⁺)

mp.: 91.2°-94.0° C.

NMR (CDCl₃, 90 Hz): δ=0.71(t, J=7.2 Hz, 3H, CH₃); 1.16-1.58 (m, 2H);2.32 (bquin, J=7.0 Hz, 1H, ##STR12## 2.61-2.99 (m, 2H); 6.89-7.47 (m,9H).

IR (Kbr disk): 1696 cm⁻¹ (ν_(C)═O)

Synthesis of 3-(2-biphenylyl)-2-ethylpropionyl chloride

A 100-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a thermometer and a NaOH trap was charged with 13.3 g(52.4 mmol) of 3-(2-biphenylyl)-2-ethylpropionic acid and 25.9 ml (355mmol) of thionyl chloride, and the resulting mixture was stirred underreflux for 2.5 hours under a nitrogen atmosphere. After the reaction wascompleted, the unreacted thionyl chloride was distilled off underreduced pressure to obtain 15.2 g of a crude product as a yellow-orangeliquid. The thus obtained acid chloride was used in the next reactionwithout further purification.

IR (Neat): 1786 cm⁻¹ (ν_(C)═O)

Synthesis of 4-ethyl-2-phenyl-1-indanone

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel, a thermometer and a NaOH trap wascharged with 8.04 g (60.3 mmol) of anhydrous aluminum chloride and 50 mlof carbon disulfide. To the mixture was dropwise added a solutioncontaining 15.2 g (52.4 mmol) of the above-obtained3-(2-biphenylyl)-2-ethyl propionyl chloride under a nitrogen atmosphereat 0° C. After the addition was completed, the temperature in the flaskwas elevated to room temperature and the reaction mixture was stirredfor 1 hour. The reaction mixture was poured onto 200 ml of ice-water andextracted with 100 ml of ether two times. The combined organic phase waswashed with 100 ml of a saturated aqueous solution of NaHCO₃ and further100 ml of a saturated aqueous solution of sodium chloride, followed bydrying over anhydrous Na₂ SO₄. The solvent was evaporated under reducedpressure. The residue was chromatographed on silica gel (eluting withhexane/ethyl acetate(10/1), parts by volume) to obtain 10.8 g of thedesired product as a yellow solid (yield: 88%).

NMR (CDCl₃, 90 MHz): δ=0.98(t, J=7.2 Hz, 3H, CH₃); 1.60-2.20 (m, 2H);2.42-2.82(m, 1H, ##STR13## 2.80(dd, J=3.8 Hz, 16.5 Hz, 1H); 3.36 (dd,J=7.6 Hz, 16.5 Hz, 1H); 7.09-7.91(m, 8H).

IR (Neat): 1705 cm⁻¹ (ν_(C)═O)

Synthesis of 2-ethyl-1-hydroxy-4-phenylindene

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with0.85 g (22.6 mmol) of sodium borohydride and 28 ml of ethanol. To themixture was dropwise added a solution containing 10.6 g (45.1 mmol) ofthe above-obtained 2-ethyl-4-phenyl-1-indanone dissolved in 20 ml ofethanol at room temperature under a nitrogen atmosphere. After theaddition was completed, the temperature of was elevated to 50° C., andthe reaction mixture was stirred for 3.5 hours. After the reaction wascompleted, the unreacted sodium borohydride was decomposed by acetone.Then, the reaction mixture was concentrated under reduced pressure, andthen dissolved in 50 ml of water and extracted with 50 ml of ether.After the organic phase was separated, the aqueous phase was extractedwith 50 ml of ether two times. The combined organic phase was washedwith 100 ml of a saturated aqueous solution of sodium chloride, followedby drying over anhydrous Na₂ SO₄. The solvent was evaporated underreduced pressure to obtain 10.67 g of the desired product as a pastypale yellow liquid (mixture of two kinds of isomers) (yield: 99%).

NMR (CDCl₃, 90 MHz): δ=1.02(t, J=7.1 Hz, 3H, CH₃); 1.31-3.28(m, 5H);4.86, 5.03(each d, each J=6.4 Hz, 5.1 Hz, total 1H, ##STR14##7.10-7.66(m, 8H).

IR (Neat): 3340 cm⁻¹ (ν_(C)═O)

Synthesis of 2-ethyl-4-phenylindene

A 300-ml four-necked round flask equipped with a stirring bar, adropping funnel and a thermometer was charged with 9.78 g (41.3 mmol) of2-ethyl-1-hydroxy-4-phenylindane, 17.2 ml (123.8 mmol) of triethylamine,0.25 g (2.1 mmol) of 4-dimethylaminopyridine and 98 ml of methylenechloride. To the mixture was dropwise added a solution containing 6.4 ml(82.5 mmol) of methanesulfonyl chloride dissolved in 6.5 ml of methylenechloride under a nitrogen atmosphere at 0° C. After the addition wascompleted, the reaction mixture was stirred for 3.5 hours at thistemperature. The reaction mixture was poured onto 250 ml of ice-water.Then, the organic phase was separated and the aqueous phase was furtherextracted with 50 ml of methylene chloride two times. The combinedorganic phase was washed with a saturated aqueous solution of NaHCO₃,and then a saturated aqueous solution of sodium chloride, followed bydrying over anhydrous Na₂ SO₄. The solvent was evaporated under reducedpressure. The residue was chromatographed on silica gel (eluting withhexane) to obtain 6.56 g of the desired product as a pale yellow liquid(mixture of two kinds of isomers)(yield: 73%).

NMR (CDCl₃, 90 MHz): δ=1.20(t, J=7.6 Hz, 3H, CH₃); 2.49(q, J=7.6 Hz,2H); 3.41(s, 2H); 6.61, 6.72(each bs, total 1H); 7.09-8.01 (m, 8H).

Synthesis of dimethylsilyl-bis(2-ethyl-4-phenylindene)

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with5.0 g (22.8 mmol) of 2-ethyl-4-phenylindene, 80 mg (0.63 mmol) of copperthiocyanate and 50 ml of anhydrous ether. To the mixture was graduallydropwise added 15.7 ml (25.1 mmol) of a 1.6M solution of n-butyl lithiumin hexane under a nitrogen atmosphere at 0° C. After the addition wascompleted, the temperature was elevated to room temperature, thereaction mixture was stirred for 1 hour. Then, to the reaction mixturewas gradually dropwise added a solution containing 1.52 ml (12.6 mmol)of dimethyldichlorosilane dissolved in 4.5 ml of anhydrous ether. Afterthe addition was completed, the reaction mixture was stirred for 12hours at room temperature. The reaction mixture was filtered throughCelite, and the filtrate was poured onto 50 ml of a saturated aqueoussolution of ammonium chloride. After the organic phase was separated,the aqueous phase was extracted with 50 ml of ether. The combinedorganic phase was washed with a saturated aqueous solution of sodiumchloride, followed by drying over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure. The residue was chromatographed onsilica gel (eluting with hexane, and hexane/methylene chloride (20/1),parts by volume) to obtain 4.5 g of the desired product (mixture of twokinds of isomers) as a pale yellow solid (yield: 80%).

NMR (CDCl₃, 90 MHz): δ=-0.23, -0.17(each s, total 6H, Si--CH₃); 1.12,1.19(each t, each J=7.4 Hz, 6H, CH₃); 2.44(bq, J=7.4 Hz, 4H); 3.81(s,2H, ##STR15## 6.75(bs, 2H, 3-H-Ind); 6.88-7.74(m, 16H).

Synthesis of rac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconiumdichloride

A 50-ml three-necked round flask equipped with a stirring bar, acondenser, a dropping funnel and a thermometer was charged with 0.84 g(1.69 mmol) of dimethylsilyl-bis(2-ethyl-4-phenylindene) and 17 ml ofanhydrous ether. To the mixture was gradually dropwise added 2.25 ml(3.56 mmol) of a 1.58M solution of n-butyl lithium in hexane at roomtemperature. After the addition was completed, the reaction mixture wasstirred for 13.5 hours. To the resulting solution was gradually added0.395 g (1.69 mmol) of ZrCl₄ at -70° C. After the addition wascompleted, the mixture was allowed to warm to room temperatureovernight. Then, the solvent was evaporated at room temperature underreduced pressure. To the resulting material was added 30 ml of methylenechloride. Then, the insoluble material was filtered off and the filtratewas concentrated and crystallized at room temperature. After theprecipitates were filtered, the residue was washed with 3 ml ofanhydrous ether two times, followed by drying under reduced pressure toobtain 0.17 g of the desired product as an orange-yellow solid (yield:15%).

NMR (CDCl₃, 90 MHz): δ=1.09(t, J=7.3 Hz, 6H, CH₃); 1.34 (s, 6H,Si--CH₃); 2.46 (quin, J=7.3 Hz, 2H) 2.73 (quin, J=7.3 Hz, 2H) 6.96 (s,2H, 3-H-Ind); 6.99-7.88 (m, 16H).

Example 2

A 2-liter gas through type-glass reactor thoroughly purged with nitrogenwas charged with 1.7 liters of toluene. The reactor was cooled to -30°C., and the reaction system was sufficiently saturated by passingthrough propylene at a flow rate of 100 liters/hr and hydrogen at a flowrate of 10 liters/hr. Then, to the reactor were added 4.25 mmol oftriisobutylaluminum, 8.5 mmol (in terms of Al atom) of methylaluminoxaneand 0.017 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-ethyl-4-plenylindenyl)}zirconium dichloride.While maintaining the temperature of the reaction system at -30° C., thepolymerization was carried out for 45 minutes. The polymerization wasstopped by the addition of a small amount of methanol. Thepolymerization suspension was added to 3 liters of methanol containing asmall amount of hydrochloric acid, which was then sufficiently stirredand filtered. The resulting polymer was washed with a large amount ofmethanol and dried at 80° C. for 10 hours.

The amount of the thus obtained polymer was 51.3 g. The polymerizationactivity was 4.02 kg-PP/mmol-Zr·hr, the intrinsic viscosity η! was 3.37dl/g, and Mw/Mn was 2.22. In the polymer, the triad tacticity was 99.7%,the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.10%, and the proportion ofthe inversely inserted units based on the 1,3-insertion of the propylenemonomer was less than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 3

The polymerization was carried out in the same manner as in Example 2except that propylene and ethylene were passed through at a flow rate of100 liters/hr and a flow rate of 2 liters/hr, respectively, 0.65 mmol oftriisobutylaluminum and 0.0026 mmol (in terms of Zr atom) of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloridewere used, and the system was maintained at 60° C., to obtain a polymer.

The amount of the thus obtained polymer was 60.7 g. The polymerizationactivity was 31.1 kg-PP/mmol-Zr·hr, the intrinsic viscosity η! was 3.01dl/g, and Mw/Mn was 2.18. In the polymer, the triad tacticity was 99.5%,the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.15%, and the proportion ofthe inversely inserted units based on the 1,3-insertion of the propylenemonomer was less than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Comparative Example 1

The polymerization was carried out in the same manner as in Example 3except that therac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloridewas used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride.

The amount of the thus obtained polymer was 4.7 g. The polymerizationactivity was 2.4 kg-PP/mmol-Zr·hr, the intrinsic viscosity η! was 4.05dl/g, and Mw/Mn was 2.18. In the polymer, the triad tacticity was 98.6%,the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.33%, and the proportion ofthe inversely inserted units based on the 1,3 insertion of the propylenemonomer was less than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 4

A 500-ml gas through type-glass reactor thoroughly purged with nitrogenwas charged with 250 ml of toluene. The reactor was cooled to 0° C., andthe reaction system was sufficiently saturated by passing throughpropylene at a flow rate of 160 liters/hr and ethylene at a flow rate of40 liters/hr. Then, to the reactor were added 0.25 mmol oftriisobutylaluminum, 0.5 mmol (in terms of Al atom) of methylaluminoxaneand 0.001 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride.While maintaining the temperature of the reaction system at 0° C., thepolymerization was carried out for 10 minutes. The polymerization wasstopped by the addition of a small amount of methanol. Thepolymerization suspension was poured onto 2 liters of methanolcontaining a small amount of hydrochloric acid, which was thensufficiently stirred and filtered. The resulting polymer was washed witha large amount of methanol and dried at 80° C. for 10 hours.

The amount of the thus obtained polymer was 5.62 g. The polymerizationactivity was 33.7 kg-polymer/mmol-Zr·hr. The ethylene content was 3.9%by mol, the intrinsic viscosity η! was 1.80 dl/g, Mw/Mn was 2.15, and Tmwas 126° C. In the polymer, the triad tacticity was 99.3%, theproportion of the inversely inserted units based on the 2,1-insertion ofthe propylene monomer was 0.12%, and the proportion of the inverselyinserted units based on the 1,3-insertion propylene monomer was lessthan the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

The film of the polymer had a heat seal-starting temperature of 129° C.and a heat seal-starting temperature after heat treatment of 132° C.

The results are shown in Table 2.

Example 5

The polymerization was carried out in the same manner as in Example 4except that the reaction system was sufficiently saturated by passingthrough propylene at a flow rate of 140 liters/hr and ethylene at a flowrate of 60 liters/hr, respectively. The thus obtained polymer solutionwas poured onto 2 liters of methanol containing a small amount ofhydrochloric acid to precipitate a polymer. The methanol wassufficiently removed, and the resulting polymer was dried at 130° C. for10 hours.

The amount of the thus obtained polymer was 6.63 g and thepolymerization activity was 39.8 kg-polymer/mmol-Zr·hr. The ethylenecontent was 8.7% by mol, the intrinsic viscosity η! was 1.66 dl/g, Mw/Mnwas 2.46, and Tm was 105° C. In the polymer, the triad tacticity was99.2%, the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.12%, and the proportion ofthe inversely inserted units based on the 1,3-insertion of the propylenemonomer was less than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

The film of the polymer had a heat seal-starting temperature of 106° C.and a heat seal-starting temperature after heat treatment of 109° C.

The results are shown in Table 2.

Example 6

The polymerization reaction was carried out in the same manner as inExample 4 except that the reaction system was sufficiently saturated bypassing through propylene at a flow rate of 100 liters/hr and ethyleneat a flow rate of 100 liters/hr, respectively. The thus obtained polymersolution was poured onto 2 liters of methanol containing a small amountof hydrochloric acid to precipitate a polymer. The methanol wassufficiently removed and the resulting polymer was dried at 130° C. for10 hours.

The amount of the thus obtained polymer was 8.95 g and thepolymerization activity was 53.7 kg-polymer/mmol-Zr·hr. The ethylenecontent was 28.9% by mol, the intrinsic viscosity η! was 1.34 dl/g, andMw/Mn was 1.95. In the polymer, the triad tacticity was 98.5%, theproportion of the inversely inserted units based on the 2,1-insertion ofthe propylene monomer was 0.09%, and the proportion of the inverselyinserted units based on the 1,3-insertion of the propylene monomer wasless than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

The copolymer had an izod impact strength of 28 kg·cm/cm and a filmimpact strength of 5300 kg·cm/cm.

The results are shown in Table 2.

Example 7 Synthesis ofrac-dimethylsilyl-bis{1-(2-ethyl-4-(1-naphthyl)indenyl)}zirconiumdichloride Synthesis of 3-(2-bromophenylyl)-2-ethylpropionic acid

A 2-liter four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 44.2 g(394 mmol) of potassium t-butoxide, 392 ml of toluene and 30 ml ofN-methylpyrrolidone. To the mixture was dropwise added a solutioncontaining 61.2 g (325 mmol) of diethyl ethylmalonate dissolved in 61 mlof toluene under a nitrogen atmosphere at 60° C. After the addition wascompleted, the reaction mixture was stirred for 1 hour at thistemperature. Then, to the resulting mixture was dropwise added asolution containing 75.4 g (302 mmol) of 2-bromobenzylbromide dissolvedin 75 ml of toluene. After the addition was completed, the temperaturewas elevated and the resulting mixture was stirred under reflux for 5hours. The reaction mixture was poured onto 300 ml of water and adjustedwith 10% sulfuric acid to pH 1. The organic phase was separated and theaqueous phase was extracted with 100 ml of ether three times. Thecombined organic phase was washed with 200 ml of a saturated aqueoussolution of sodium bicarbonate and then 150 ml of a saturated aqueoussolution of sodium chloride three times, followed by drying overanhydrous Na₂ SO₄. The solvent was concentrated under reduced pressureto obtain 111.1 g of a concentrate as a yellow liquid.

A 2-liter four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 195 g(2.96 mol) of potassium hydoxide and 585 ml of an aqueous solution ofmethanol (methanol/water=4/1(v/v)). To the mixture was dropwise addedthe above-obtained concentrate at room temperature under a nitrogenatmosphere. After the addition was. completed, the temperature waselevated and the resultant mixture was stirred under reflux for 3 hours.Thereafter, the temperature was cooled to room temperature and theprecipitated white solid was filtered. The filtrate was concentrated andcooled to obtain a second crop. The same procedure was repeated asdescribed above to obtain a third crop. The combined crops were slurriedin hexane and filtered. The solid thus obtained was dried to obtain101.5 g of a white powder. The white powder was dissolved in 400 ml ofwater and the resulting solution was acidified with addition of 50% H₂SO₄ aq. to pH 1. The resulting mixture was extracted with 200 ml ofmethylene chloride five times. The combined organic phase was dried overanhydrous Na₂ SO₄. The solvent was concentrated under reduced pressureto obtain 74.2 g of a hard white solid.

Then, a 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a thermometer was charged with the above-obtainedwhite solid. Then, the solid was heated to 200° C. and stirred for 5hours under a nitrogen atmosphere. After the reaction was completed, thereaction product was cooled to room temperature to obtain 61.2 g of thedesired product as a pale yellow-white solid (yield: 79%).

FD-MS: 256 (M⁺), 258 (M⁺ +2)

NMR (CDCl₃, 90 MHz): δ=1.0(t, J=7.0 Hz, 3H, CH₃); 1.40-1.85(m, 2H);2.53-3.12(m, 3H); 6.88, 7.66(m, 3H).

Synthesis of 3-(2-bromophenyl)-2-ethylpropionyl chloride

A 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a thermometer and a NaOH trap was charged with 60.86g (237 mmol) of 3-(2-bromphenylyl)-2-ethylpropionic acid, 40 ml ofbenzene and 120 ml of thionyl chloride, and the mixture was stirredunder reflux for 1.5 hours under a nitrogen atmosphere. After thereaction was completed, the unreacted thionyl chloride was distilled offunder reduced pressure to obtain the crude product as a yellow liquid.The thus obtained acid chloride was used in the next reaction withoutfurther purification.

Synthesis of 4-bromo-2-ethyl-1-indanone

A 1-liter three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel, a thermometer and a NaOH trap wascharged with 36.3 g (272 mmol) of anhydrous aluminum chloride and 280 mlof carbon disulfide. To the mixture was dropwise added a solutioncontaining the above obtained 3-(2-bromophenyl)-2-ethylpropionylchloride dissolved in 50 ml of carbon disulfide under a nitrogenatmosphere at 0° C. After the addition was completed, the temperature inthe flask was elevated to room temperature and the reaction mixture wasstirred for 1 hour. The reaction mixture was poured onto 1 liter ofice-water and extracted with 300 ml of ether two times. The combinedorganic phase was washed with a saturated aqueous solution of NaHCO₃,and then a saturated aqueous solution of sodium chloride, followed bydrying over anhydrous Na₂ SO₄. The solvent was evaporated under reducedpressure to obtain 56.9 g of the desired product as a slightly pastyred-brown liquid. The thus obtained ketone was used in the next reactionwithout further purification.

Synthesis of 4-bromo-2-ethyl-1-trimethylsilyloxyindane

A 500-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with4.97 g (118 mmol) of sodium borohydride and 200 ml of ethanol. To themixture was dropwise added a solution containing 56.93 g of theabove-obtained 4-bromo-2-ethyl-1-indanone dissolved in 85 ml of ethanolat room temperature under a nitrogen atmosphere. After the addition wascompleted, the reaction mixture was stirred for additonal 4 hours. Afterthe reaction was completed, the reaction mixture was cooled and theunreacted sodium borohydride was decomposed by acetone. Then, thereaction mixture was concentrated under reduced pressure, and dissolvedin 300 ml of water and extracted 300 ml of ether. After the organicphase was separated, the aqueous phase was extracted with 100 ml ofether three times. The combined organic phase was washed three timeswith 150 ml of a saturated aqueous solution of sodium chloride, followedby drying over anhydrous Na₂ SO₄. The solvent was evaporated underreduced pressure to obtain 58.92 g of a flesh colored solid.

A 500-ml four-necked round flask equipped with a stirring bar, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 58.91 g(244 mmol) of the above-obtained solid, 43.3 ml (307 mmol) oftriethylamine and 280 ml of methylene chloride. To the mixture wasgradually dropwise added a solution containing 37.2 ml (293 mmol) of Me₃SiCl dissolved in 15 ml of methylene chloride under a nitrogenatmosphere at 0° C. After the addition was completed, the temperaturewas elevated to room temperature, and the reaction mixture was stirredfor additional 3.5 hours. The reaction mixture was poured onto 100 ml ofwater. Then, the organic phase was separated and the aqueous phase wasextracted with 100 ml of methylene chloride two times. The combinedorganic phase was washed with 100 ml of water three times, followed bydrying over anhydrous Na₂ SO₄. The solvent was evaporated under reducedpressure. The residue was distilled under reduced pressure to obtain69.9 g of the desired product (mixture of two isomers) as a colorlessliquid (total yield: 95% from 3-(2-bromophenylyl)-2-ethylpropionicacid).

mp.: 133°-135° C./2 mmHg

FD-MS: 312 (M⁺), 314(M⁺ +2)

NMR (CDCl₃, 90 MHz): δ=0.17, 0.24(each s, total 9H, Si--CH₃);0.79-1.12(m, 3H); 1.16-3.31(m, 5H); 4.82, 5.10(each bd, each J=6.4 Hz,total 1H, --CH--O--); 6.91-7.46 (m, 3H).

Synthesis of 2-ethyl-4-(1-naphthyl)phenylindene

A 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with11.4 g (36.4 mmol) of 4-bromo-2-ethyl-1-trimetylsilyloxyindane, 0.13 g(0.18 mmol) of PdCl₂ (dppf) and 35 ml of anhydrous ether. To theresulting mixture was dropwise added 101 ml (72.8 mmol) of a 0.72Msolution of 1-naphthylmagnesiumbromide in ether/benzene at roomtemperature under a nitrogen atmosphere. After the addition wascompleted, the reaction mixture was stirred for 1 hour. Then, thetemperature in the flask was elevated to 50° to 51° C., and the reactionmixture was stirred for additional 5 hours. After the reaction wascompleted, to the reaction mixture was added 135 ml of 5N hydrochloricacid at 0° C. to decompose the excess amount of Grignard reagent, andthe resulting mixture was extracted with 100 ml of ether two times. Thecombined organic phase was washed with a saturated aqueous solution ofsodium bicarbonate, and then a saturated aqueous solution of sodiumchloride, followed by drying over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure to obtain 20.5 g of a product as ared-brown liquid.

Then, the above-obtained red-brown liquid was diluted with 20 ml oftetrahydrofuran. To the mixture was added 5 ml of 12% hydrochloric acidand the reaction mixture was stirred at room temperature overnight.After the reaction was completed, to the reaction mixture was added 100ml of ether and the organic phase was separated. The organic phase waswashed with a saturated aqueous solution of sodium bicarbonate, and thena saturated aqueous solution of sodium chloride, followed by drying overanhydrous Na₂ SO₄. The solvent was evaporated under reduced pressure.The residue was chromatographed on silica gel (Silica gel 60 from MERCKCo., 70-230 mesh, eluting with hexane, and then hexane/ethylacetate(1/3, parts by volume)) to obtain 9.0 g of the desired product(mixture of two isomers) as a yellow solid (yield: 98%).

FD-MS: 270 (M⁺)

NMR (CDCl₃, 90 MHz): δ=1.20(t, J=7.4 Hz, 3H, CH₃); 2.38(bq, J=7.4 Hz,2H); 3.02, 3.42(each s, total 2H); 6.54(bs, 1H); 6.19-8.12 (m, 10H)

Synthesis of dimethylsilyl-bis{1-(2-ethyl-4-(1- naphthyl)indene)}

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with4.97 g (18.4 mmol) of 2-ethyl-4-(1-naphthyl)indene, 50 mg (0.51 mmol) ofcopper cyanide and 53 ml of anhydrous ether. To the mixture wasgradually dropwise added 12.8 ml (20.2 mmol) of a 1.58M solution ofn-butyl lithium in hexane under a nitrogen atmosphere at -10° C. Afterthe addition was completed, the temperature was elevated to roomtemperature and the reaction mixture was stirred for 4 hours. Then, tothe reaction mixture was gradually dropwise added a solution containing1.24 ml (10.1 mmol) of dimethyldichlorosilan dissolved in 5 ml ofanhydrous ether. After the addition was completed, the reaction mixturewas stirred for 15 hours at room temperature. The reaction mixture waspoured onto 50 ml of a saturated aqueous solution of ammonium chlorideand filtered through Celite. The organic phase was separated and theaqueous phase was extracted with 50 ml of ether. The combined organicphase was washed with a saturated aqueous solution of sodium chloride,followed by drying over anhydrous Na₂ SO₄. The solvent was evaporatedunder reduced pressure. The residue was chromatographed on silica gel(eluting with hexane) to obtain 3.2 g of the desired product (mixture oftwo isomers) as a yellow solid (yield: 58%).

FD-MS: 596 (M⁺)

NMR (CDCl₃, 90 MHz): δ=-0.20, -0.20(each s, total 6H, Si--CH₃);0.82-1.41(m, 6H, CH₃); 2.23, 2.74(m, 4H); 3.84-4.10(m, 2H, --CH--Si);6.20, 6.30(each bd, 2H); 6.98-8.14 (m, 20H)

Synthesis of rac-dimethylsilyl-bis{1-(2-ethyl-4-(1-naphthyl)indenyl)}zirconium dichloride

A 100-ml three-necked round flask equipped with a stirring bar, acondenser having beads, a dropping funnel and a thermometer was chargedwith 2.0 g (3.36 mmol) of dimethylsilyl-bis(2-ethyl-4-(1-naphthyl)indeneand 40 ml of anhydrous ether under an argon atmosphere. To the mixturewas gradually dropwise added 4.58 ml (7.06 mmol) of a 1.54M solution ofn-butyl lithium in hexane at room temperature. After the addition wascompleted, the reaction mixture was stirred for 17.5 hours. Theresulting reaction solution was cooled to -75° C. Then, to the solutionwas gradually added 0.83 g (3.56 mmol) of ZrCl₄. After the addition wascompleted, the mixture was allowed to warm to room temperatureovernight.

The thus obtained red-yellow reaction slurry was filtered, and washedwith 45 ml of anhydrous ether. To the residue were added 60 ml ofmethylene chloride and 40 ml of anhydrous ether, and then the insolublematerial was filtered off. The filtrate was concentrated to dryness atroom temperature. The residue was dissolved in 15 ml of methylenechloride and concentrated to about 1/3 of total volume of the mixture.Then, 2 ml of anhydrous ether to give the precipitate. The precipitatewas filtered and washed with 2 ml of anhydrous ether, followed by dryingunder a reduced pressure to obtain 0.12 g of the desired product as ayellow-orange powder (yield: 5%).

NMR (CDCl₃, 90 MHz): δ=1.04(t, J=7.4 Hz, 6H, CH₃); 1.38 (s, 6H,Si--CH₃); 2.12-3.02 (m, 4H); 6.53 (s, 2H, 3-H-Ind); 6.86-8.02 (m, 20H).

Example 8

The polymerization was carried out in the same manner as in Example 3except that therac-dimethylsilyl-bis{1-(2-ethyl-4-(1-naphthyl)indenyl)}zirconiumdichloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component.

The amount of the thus obtained polymer was 20.2 g and thepolymerization activity was 10.4 kg-PP/mmol-Zr·hr. The intrinsicviscosity η! was 3.08 dl/g, and Mw/Mn was 2.09. In the polymer, thetriad tacticity was 99.7%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.12%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was less than the detectablelower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 9

The polymerization reaction was carried out in the same manner as inExample 5 except that therac-dimethylsilyl-bis{1-(2-ethyl-4-(1-naphthyl)indenyl)}zirconiumdichloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component.

The amount of the thus obtained polymer was 2.08 g and thepolymerization activity was 12.5 kg-polymer/mmol-Zr·hr. The ethylenecontent was 7.9% by mol, the intrinsic viscosity η! was 1.39 dl/g, Mw/Mnwas 2.33, and Tm was 109° C. In the polymer, the triad tacticity was99.2%, the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.10%, and the proportion ofthe inversely inserted units based on the 1,3-insertion of the propylenemonomer was less than the detectable lower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

The film of the polymer had a heat seal-starting temperature of 106° C.and a heat seal-starting temperature after heat treatment of 110° C.

The results are shown in Table 2.

Example 10 Synthesis of rac-dimethylsilyl-bis{1-(2-n-propyl-4-(1-naphthyl)indenyl}zirconium dichloride Synthesis of3-(2-bromophenyl)-2-n-propyloropionic acid

A 1-liter four-necked round flask equipped with a 25 stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 37 g(330 mmol) of potassium t-butoxide, 32 ml (334 mmol) ofN-methylpyrrolidone and 400 ml of toluene. To the mixture was addeddropwise a solution containing 60.7 g (300 mmol) of n-diethylpropylmalonic acid dissolved in 50 ml of toluene at the reactiontemperature of 5° to 10° C. for 30 minutes with stirring in an ice bath.After the addition was completed, the mixture was stirred at 45° C. for30 minutes and at 65° C. for additional 1 hour. The resulting solutionturned a cream colored heterogeneous material immediately after heating.

To the resultant material was added dropwise a solution containing 75 g(300 mmol) of 2-bromobenzylbromide dissolved in 50 ml of toluene at thereaction temperature of 5° to 15° C. for 30 minutes in an ice bath.After the addition was completed, the mixture was stirred at 65° C. for30 minutes. The temperature was elevated and the reaction mixture washeated under reflux for 1 hour. The color of the reaction product wasgradually changed to gray. After allowing to cool, the reaction productwas poured onto 500 ml of water and the mixture was controlled to pH 1with addition of an aqueous solution of 10% sulfuric acid. The organicphase was separated and the aqueous phase was extracted with 100 ml oftoluene five times. The combined organic phase was washed with 200 ml ofNaCl aq. four times, followed by drying over MgSO₄. The solvent wasevaporated to give 114 g of a brown liquid.

A 1-liter four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with theabove-obtained liquid and 200 ml of methanol, and stirred. To themixture was added a solution containing 237 g (content: 85%, 3.59 mol)of potassium hydroxide dissolved in 520 ml of methanol and 180 ml ofwater. Then, this flask was heated at 90° C. and the mixture wasrefluxed for 5 hours. Thereafter, almost of the methanol was evaporatedusing an evaporator and 500 ml of water was added thereto to give ahomogeneous solution. While cooling with ice, the homogeneous solutionwas controlled to pH 1 with addition of an aqueous solution of 10%sulfuric acid. The resultant white precipitate was separated byfiltration. Then, the organic phase was separated from the filtrate, andthe aqueous phase was extracted with 200 ml of ether six times. Thecombined organic phase was dried over anhydrous MgSO₄. The solvent wasevaporated to give 94 g of a yellow-white semisolid.

Then, the semisolid was charged into 1-liter round flask, and heated for10 minutes at 180° C. After heating, the resulting product was cooled togive 78.0 g of the desired product as a brown transparent liquid (yield:96%).

FD-MS: 270 (M⁺), 272 (M⁺ +2)

NMR (CDCl₃, 90 MHz): δ=0.95 (t, J=7.0 Hz, 3H, CH₃); 1.10-2.00 (m, 4H);2.60-3.25 (m, 3H); 6.90-7.80 (m, 4H)

Synthesis of 3-(bromophenyl)-2-n-propylpropionyl chloride

A 500-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a thermometer and a NaOH trap was charged with 277mmol of 3-(2-bromophenyl)-2-propylpropionic acid and 200 ml of thionylchloride, and the mixture was heated under reflux for 2 hours. Then, theexcess thionyl chloride was removed by a single distillation, and thedistillation of the residue under reduced pressure gave 77.4 g of acrude product having a boiling point of 130° to 135° C./1 mmHg as a palebrown transparent liquid. This acid chloride was used in the nextreaction without further purification

Synthesis of 4-bromo-2-n-propyl-1-indanone

A 1-liter four-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel, a thermometer and a NaOH trap wascharged with 74.5 g (559 mmol) of anhydrous aluminum chloride and 400 mlof carbon disulfide. To the mixture was added gradually dropwise asolution containing the above-obtained acid chloride dissolved in 100 mlof carbon disulfide while cooling with ice bath. After the addition wascompleted, the mixture was stirred at 0° C. for 3 hours. Then, thereaction solution was poured onto 600 ml of ice water. The organic phasewas separated and the aqueous phase was extracted with 200 ml of etherfour times. The combined organic phase was washed four times with 300 mlof a saturated aqueous solution of sodium bicarbonate, followed bydrying over anhydrous MgSO₄. The solvent was evaporated to give 66.7 gof a brown liquid. This ketone was used in the next reaction withoutfurther purification.

Synthesis of 4-bromo-2-n-propyl-1-trimethylsilyloxyindane

A 1-liter four-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with4.96 g (131 mmol) of sodium born hydride and 300 ml of ethanol. To themixture was added dropwise a solution containing the above-obtained4-bromo-2-n-propyl-1-indanone dissolved in 200 ml of ethanol whilecooling with ice bath. After the addition was completed, the mixture wasstirred for 3 hours at room temperature. After the reaction wascompleted, to the reaction mixture was added 200 ml of ice water and thealmost of the methanol was evaporated using an evaporator. The residuewas transferred to a separating funnel using 300 ml of ether. After theorganic phase was separated, the aqueous phase was extracted with 200 mlof ether three times. The combined organic phase was dried overanhydrous MgSO₄. Then, the solvent was evaporated to give 66.50 g of ayellow-white powder.

Then, the above-obtained yellow-white powder, 200 ml of ether and 47 ml(337 mmol) of triethylamine were charged into a 1-liter four-neckedround flask. To the mixture was added a solution containing 39 ml (307mmol) of trimethylsilyl chloride dissolved in 50 ml of ether whilecooling with ice bath. After the reaction mixture was stirred for 7hours, the reaction mixture was poured onto 400 ml of a saturatedaqueous solution of sodium bicarbonate, and the organic phase wasseparated. Then, the aqueous phase was extracted with 200 ml of etherthree times. The combined organic phase was washed with 400 ml of asaturated NaCl aq., followed by dried over anhydrous MgSO₄. Then, thesolvent was evaporated to give a yellow-brown liquid. The liquid wasdistilled under reduced pressure to give 76.00 g of the desired productas a pale yellow-white transparent liquid having a boiling point of 120°to 125° C./2 mmHg. The total yield of this liquid was 81% from the3-(2-bromophenyl)-2-n-propylpropionic acid.

Synthesis of 2-n-propyl-4-(1-naphthyl)indene

A 300-ml four-necked round flask equipped with a stirring bar, adropping funnel and a thermometer was charged with 10 g (30.5 mmol) of4-bromo-2-n-propyl-1-trimethylsilyloxyindane, 50 ml of dry ether and 112mg (0.153 mmol) of PdCl₂ (dppf). To the mixture was added graduallydropwise 85 ml (61 mmol) of an ether/benzene solution containing 0.72M1-naphthyl magnesium bromide at room temperature. Then, the temperaturein the flask was elevated to 48° C. and the mixture was stirred underreflux for 4 hours. Thereafter, the reaction product was poured onto 300ml of a saturated aqueous solution of ammonium chloride, which was thenextracted with 200 ml of ether four times. The organic phase was washedwith a saturated NaCl aq., followed by dried over anhydrous MgSO₄. Thesolvent was evaporated to give 17.83 g of a yellow-brown semisolid.

The above-obtained yellow-brown semisolid and 50 ml of ether werecharged into a 300-ml three-necked round flask. To the mixture was addeddropwise 60 ml of an aqueous solution of 5N hydrochloric acid at roomtemperature, and vigorously stirred. After 2 hours, the mixture wastransferred to a separating funnel and extracted with 50 ml of etherthree times. The combined organic phase was washed with 100 ml of asaturated aqueous solution of sodium bicarbonate two times, followed bydried over anhydrous MgSO₄. The solvent was evaporated to give a brownsemisolid. The semisolid thus obtained was purified with silica gelchromatography (eluting with hexane/ethyl acetate=50/1 to 50/5) to give8.40 g of a yellow-white powder.

Then, the above-obtained yellow-white powder, 80 ml of anhydrousmethylene chloride, 11.3 ml (81 mmol) of triethylamine and 165 ml (1.35mmol) of 4-dimethylaminopyridine were charged into a 200-ml four-neckedround flask. To the mixture was added gradually dropwise a solutioncontaining 4.2 ml (54.3 mmol) of methanesulfonyl chloride dissolved in20 ml of anhydrous methylene chloride while cooling with ice bath. Afterthe addition was completed, the temperature was elevated to roomtemperature, and the mixture was stirred overnight. Then, the reactionproduct was poured onto 100 ml of ice water, which was then extractedwith 100 ml of methylene chloride three times. The combined organicphase was washed with 100 ml of a saturated aqueous solution of sodiumbicarbonate three times, followed by dried over anhydrous MgSO₄. Thesolvent was evaporated to give a brown liquid. The thus obtained brownliquid was chromatographed on silica gel (200 g of silica gel,hexane/ethyl acetate=50/1) to give 6.51 g of the desired product as awhite solid (yield: 75%).

NMR (CDCl₃, 90 MHz): δ=0.91 (t, J=7.0 Hz, 3H, CH₃); 1.53 (m, 2H); 2.40(t, J=7.0 Hz, 2H); 3.04, 3.41 (each s, total 2H); 6.60 (s, 1H) 7.00-8.00(m, 10H)

Synthesis of dimethylsilyl-bis{1-(2-n-propyl-4-(1-naphthyl)indene

A 200-ml four-necked round flask equipped with a stirring bar, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 6.27 g(22.0 mmol) of 2-n-propyl-4-(1-naphthyl)indene, 120 ml of dry ether and60 mg of copper cyanide. To the mixture was added dropwise 15 ml (24.5mmol) of a hexane solution containing 1.63M n-butyl lithium whilecooling with ice bath. After the addition was completed, the mixture wasstirred under reflux for 30 minutes. Then, to the resulting mixture wasadded dropwise a solution containing 1.5 ml (12.4 mmol) ofdimethyldichlorosilane dissolved in 5 ml of dry ether while cooling withice bath. After the addition was completed, the mixture was stirredovernight at room temperature. Then, the reaction mixture was pouredonto a saturated aqueous solution of ammonium chloride. Afterfiltration, the organic phase of the filtrate was separated, and theaqueous phase was extracted with 50 ml of ether two times. The combinedorganic phase was washed with 100 ml of a saturated NaCl aq. two times,followed by dried over anhydrous MgSO₄. The solvent was evaporated togive a yellow oil. The yellow oil thus obtained was then purified withsilica gel chromatography (200 g of silica gel, hexane/ethylacetate=50/1) to give 5.80 g of of the desired product as a yellow-whitepowder (yield: 84%).

NMR (CDCl₃, 90 MHz): δ=-0.20, -0.17 (each s, total 6H, Si--CH₃);0.64-2.70 (m, 14H); 3.80-4.10 (m, 2H, --CH--Si); 6.25, 6.34 (each 6d,total 2H); 7.20-8.20 (m, 20H)

Synthesis ofrac-dimethylsilyl-bis{1-(2-n-propyl-4-(1-naphthyl)indenyl)}zirconiumdichloride

A 100-ml four-necked round flask equipped with a stirring bar, acondenser, a dropping funnel and a thermometer was charged with 2.5 g(4.00 mmol) of dimethylsilyl-bis{1-(2-n-propyl-4-(1-naphthyl)indene} and50 ml of dry ether. To the mixture was added dropwise 5.15 ml (8.40mmol) of a hexane solution containing 1.63M n-butyl lithium in a waterbath. After the addition was completed, the mixture was stirredovernight at room temperature. Thereafter, to the resulting mixture wasadded 1.00 g (4.29 mmol) of ZrCl₄ at -78° C. After the addition wascompleted, the mixture was allowed to stand overnight. The resultantorange color reaction slurry was filtered and the filtered material waswashed with 40 ml of dry ether and 40 ml of dry methylene chloride. Themixture was filtered and the filtrate was concentrated to about 1/3 of atotal volume of the filtrate. The precipitate was dissolved in 10 ml ofmethylene chloride, which was then crystallized from 20 ml of dry ether.The precipitate was filtered and washed with 5 ml of dry ether, followedby dried under reduced pressure to give 0.09 g of the desired product asthe yellow powder (yield: 3%).

NMR (CDCl₃, 90 MHz): δ=0.80 (t, J=7.4 Hz, 6H, CH₃); 1.36 (s, 6H,Si--CH₃); 1.10-3.00 (m, 8H); 6.53 (s, 2H, 3-H-Ind); 7.00-8.00 (m, 20H)

Example 11 Synthesis ofrac-dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride Synthesis of 2-n-propyl-4-(9-phenanthryl)indene

A 300-ml four-necked round flask equipped with a stirring bar, adropping funnel and a thermometer was charged with 10 g (30.5 mmol) ofthe 4-bromo-2-n-propyl-1-trimethylsilyloxyindane synthesized in Example10, 50 ml of dry ether and 112 mg (0.153 mmol) of PdCl₂ (dppf). To themixture was added dropwise 42 ml (61 mmol) of an ether/benzene solutioncontaining 1.45M 9-phenantolyl magnesium bromide at room temperaturewhile stirring. Then, the temperature in the flask was elevated to 42°C. and the mixture was stirred under reflux for 10 hours. Thereafter,the reaction mixture was poured onto 300 ml of a saturated aqueoussolution of ammonium chloride, which was then extracted with 200 ml ofether four times. The combined organic phase was washed with a saturatedNaCl aq. and dried over anhydrous MgSO₄. The solvent was evaporated togive 20.3 g of a brown liquid.

The above-obtained brown liquid and 50 ml of ether were charged into a300-ml four-necked round flask. To the flask was added dropwise 60 ml ofan aqueous solution of 5N hydrochloric acid at room temperature, and themixture was vigorously stirred for 6.5 hours. The resulting mixture wastransferred to a separating funnel, and washed with 50 ml of ether fourtimes. The combined organic phase was washed with 100 ml of a saturatedaqueous solution of sodium bicarbonate two times, followed by dried overanhydrous MgSO₄. The solvent was evaporated to give a brown semisolid.The brown semisolid thus obtained was purified with silica gelchromatography to give 10.75 g of a yellow powder.

Then, the above-obtained yellow powder, 80 ml of anhydrous methylenechloride, 12.8 ml (92.0 mmol) of triethylamine and 187 ml (1.53 mmol) of4-dimethylaminopyridine were charged into a 200-ml four-necked roundflask. To the mixture was added dropwise a solution containing 4.72 ml(61.0 mmol) of methanesulfonyl chloride dissolved in 20 ml of anhydrousmethylene chloride while cooling with ice bath. After the addition wascompleted, the temperature was elevated to room temperature and themixture was stirred for four hours. Thereafter, the reaction product waspoured onto 100 ml of ice water, which was then extracted with 100 ml ofmethylene chloride three times. The combined organic phase was washedwith 100 ml of a saturated aqueous solution of sodium bicarbonate threetimes, followed by dried over anhydrous MgSO₄. The solvent wasevaporated to give a red-brown semisolid. The red-brown semisolid thusobtained was purified with silica gel chromatography to give 7.20 g ofthe desired product as a yellow-white powder (yield: 71%).

NMR (CDCl₃, 90 MHz): δ=0.92 (t, J=7.0 Hz, 3H, CH₃); 1.50 (m, 2H); 2.36(t, J=7.0 Hz, 2H); 3.02 (bd, 2H); 6.60 (s, 1H); 7.05-9.00 (m, 12H)

Synthesis of dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indene

A 300-ml four-necked round flask equipped with a stirring bar, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 6.20 g(18.5 mmol) of 2-n-propyl-4-(9-phenantolyl)indene, 120 ml of dry etherand 50 mg of copper cyanide. To the mixture was added dropwise 12.5 ml(20.4 mmol) of a hexane solution containing 1.63M n-butyl lithium whilecooling with ice bath. After the addition was completed, the mixture wasstirred under reflux for 1.5 hours. Then, to the resulting mixture wasadded dropwise a solution containing 1.34 ml (11.1 mmol) ofdimethyldichlorosilan dissolved in 10 ml of dry ether. After theaddition was completed, the mixture was stirred overnight at roomtemperature. Then, the reaction mixture was poured onto 200 ml of asaturated aqueous solution of ammonium chloride. After the filtration,the filtrate was extracted with 100 ml of ether three times. The organicphase was washed with 200 ml of a saturated NaCl aq. and dried overanhydrous MgSO₄. The solvent was evaporated to give a yellow-whitepowder. The powder thus obtained was purified with silica gelchromatography to give 3.80 g of the desired product as a yellow-whitepowder (yield: 54%).

NMR (CDCl₃, 90 MHz): δ=-0.17, -0.15 (each s, total 6H, Si--CH₃);0.65-2.75 (m, 14H); 3.86-4.25 (m, 2H, --CH--Si); 6.25, 6.34 (each 6d,2H); 7.05-9.05 (m, 24H)

Synthesis ofrac-dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride

A 200-ml four-necked round flask equipped with a stirring bar, acondenser having beads, a dropping funnel and a thermometer was chargedwith 2.9 g (4.00 mmol) ofdimethylsilyl-bis{1-(2-n-propyl-4-(9-phenantolyl)indene)} and 60 ml ofdry ether. To the mixture was added dropwise 5.15 ml (8.40 mmol) of ahexane solution containing 1.63M n-butyl lithium while cooling with icebath. After the addition was completed, the mixture was stirredovernight at room temperature. Then, to the resulting mixture was addeddropwise 1.00 g (4.29 mmol) of ZrCl₄ at -78° C. After the addition wascompleted, the mixture was allowed to warm to room temperature. Theresulting orange color reaction mixture was filtered and washed with 100ml of dry methylene chloride. The filtrate was concentrated to dryness,which was then dissolved in 100 ml of dry methylene chloride. To thesolution was added dry ether to give precipitate which was then filteredand washed with 15 ml of dry ether, followed by dried under reducedpressure to give 0.10 g of the desired product as a yellow powder(yield: 2.8%).

NMR (CDCl₃, 90 MHz): δ=0.80 (t, J=7.4 Hz, 6H, CH₃); 1.39 (s, 6H,Si--CH₃); 1.10-3.00 (m, 8H); 6.61 (s, 2H, 3-H-Ind); 7.00-9.10 (m, 24H)

Example 12 Synthesis ofrac-dimethylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride Synthesis of 2-ethyl-1-hydroxy-4-(9-phenanthryl)indane

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with11.54 g (36.8 mmol) of 4-bromo-2-ethyl-1-trimethylsilyloxyindane, 0.135g (0.184 mmol) of PdCl₂ (dppf) and 35 ml of dry ether. To the mixturewas added dropwise 51.5 ml (73.7 mmol) of an ether/benzene solutioncontaining 1.4M 9-phenantolyl magnesium bromide at room temperatureunder a nitrogen atmosphere. After the addition was completed, thetemperature in the flask was elevated to 42° C., and the mixture wasstirred under reflux for 8 hours. After the reaction was completed, thereaction mixture was cooled to room temperature, and the excess amountof Gringnard reagent was decomposed by gradually adding 100 ml of water.After the addition of 50 ml of ether, organic phase was separeted,filtered through Celite, and the filtrate was washed with 100 ml of asaturated NaCl aq., followed by dried over anhydrous Na₂ So₄. Thesolvent was evaporated under reduced pressure to give 25 g of a darkred-brown liquid.

Then, a 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged withthe above-obtained red-brown liquid and 50 ml of tetrahydrofuran. To themixture was added dropwise 6 ml of an aqueous solution of 12%hydrochloric acid at room temperature under a nitrogen atmosphere. Thereaction mixture was stirred for 5 hours. After the reaction wascompleted, 100 ml of ether was added and the organic phase wasseparated, washed with 100 ml of a saturated aqueous solution of sodiumbicarbonate, and then 100 ml of a saturated aqueous solution of saltthree times, followed by dried over anhydrous Na₂ SO₄. The solvent wasevaporated to give a dark red liquid residue. The thus obtained dark redliquid residue was purified with silica gel chromatography (eluting withhexane, and then hexane/ethyl acetate(4/1 parts by volume)) to give12.33 g of the desired product (mixture of two isomers) as a pastyred-brown liquid (yield: 99%).

FD-MS: 338 (M⁺)

Synthesis of 2-ethyl-4-(9-phenanthryl)indene

A 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with12.3 g (36.3 mmol) of 2-ethyl-1-hydroxy-4-(9-phenanthryl)indane, 19.7 ml(142 mmol) of triethylamine and 61.5 ml of methylene chloride. To themixture was gradually dropwise added a solution containing 3.3 ml (42.6mmol) of methansulfonyl chloride dissolved in 5 ml of methylene chlorideunder a nitrogen atmosphere at 0° C. After the addition was completed,the temperature was elevated to room temperature, and the reactionmixture was stirred for additional 4 hours. To the reaction mixture wasadded 80 ml of a saturated aqueous solution of sodium bicarbonate. Theorganic phase was separated, and the aqueous phase was extracted with 50ml of methylene chloride two times. The combined organic phase waswashed with water, and then a saturated aqueous solution of sodiumchloride, followed by drying over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure. The residue was chromatographed onsilica gel (eluting with hexane, and hexane/ethyl acetate(100/3 parts byvolume)) to give 9.61 g of the desired product (mixture of two isomers)as a pasty pale yellow-green liquid (yield: 83%).

FD-MS: 320 (M⁺)

NMR (CDCl₃, 90 MHz): δ=0.86-1.44 (m, 3H, CH₃); 2.16-2.58 (m, 2H); 3.04,3.42 (each bs, total 2H); 6.09, 6.55 (each bs, total 1H); 6.95-7.97 (m,10H); 8.57-8.93 (m, 2H)

Synthesis of dimethylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indene)}

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with5.3 g (16.5 mmol) of 2-ethyl-4-(9-phenanthryl)indene, 45 mg (0.45 mmol)of copper cyanide and 106 ml of dry ether. To the mixture was addeddropwise 11.8 ml (18.2 mmol) of a hexane solution containing 1.54Mn-butyl lithium under a nitrogen atmosphere at -10° C. After theaddition was completed, the temperature was elevated to room temperatureand the mixture was further stirred for 5 hours. Then, to the reactionmixture was added dropwise a solution containing 1.12 ml (9.1 mmol) ofdimethyldichlorosilane dissolved in 5 ml of dry ether while cooling withice bath. After the addition was completed, the temperature was elevatedto room temperature, and the mixture was stirred for 15 hours. To thereaction mixture was added 50 ml of a saturated aqueous solution ofammonium chloride. Then, the insoluble substance was filtered throughCelite, and the filtrate was separated to an organic phase and anaqueous phase. The aqueous phase was extracted with 50 ml of ether. Thecombined organic phase was washed with 50 ml of a saturated NaCl aq.three times, and dried over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure to obtain a residue of a pasty paleyellow-brown liquid. The thus obtained residue was separated with silicagel chromatography (eluting with hexane, and hexane/ethyl acetate(1000/7parts by volume)) to give 3.19 g of the desired product (mixture ofstereoisomers) as a yellow solid (yield: 55%).

FD-MS: 697 (M⁺)

NMR (CDCl₃, 90 MHz): δ=-0.18, -0.14 (each s, total 6H, Si--CH₃);0.79-1.41 (m, 6H, CH₃); 2.13-2.73 (m, 4H); 3.84-4.15 (m, 2H, ##STR16##6.21, 6.31 (each bs, 2H); 6.98-8.05 (m, 20H); 8.52-8.93 (m, 4H)

Synthesis ofrac-dimethylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride

A 100-ml three-necked round flask equipped with a stirring bar, acondenser, a dropping funnel and a thermometer was charged with 0.60 g(0.86 mmol) of dimethylsilyl-bis{1-(2-ethyl-4-(9-phenanthryl)indene)}and 12 ml of dry ether under an argon atmosphere. To the mixture wasadded dropwise 1.18 ml (1.81 mmol) of a hexane solution containing 1.54Mtemperal lithium at room temperature. After the addition was completed,the mixture was further stirred for 18.5 hours. The pale yellow-orangereaction mixture was cooled to -70° C. Then, to the mixture was added0.20 g (0.86 mmol) of ZrCl₄. After the addition was completed, themixture was allowed to warm to room temperature overnight. The resultingorange-yellow reaction slurry was filtered, and the residue was washedwith 6 ml of dry ether, and then 5 ml of methylene chloride five times.To the resulting product was added 55 ml of methylene chloride, and thenthe insoluble material was filtered off. The filtrate was concentratedto dryness. The dried product was reslurried in 2 ml of dry ether anddried to obtain 80 mg of a yellow-orange powder. NMR analysis showedthat this powder comprises a mixture of rac/meso (91/9). Then, theabove-obtained powder was reslurried and washed in 2 ml of methylenechloride and 2 ml of dry ether. Then, the resulting product was driedunder reduced pressure to obtain 66 mg of the desired product as ayellow-orange powder (yield: 9%).

NMR (CDCl₃, 90 MHz): δ=1.01 (t, J=7.6 Hz, 6H, CH₃); 1.37 (s, 6H,Si--CH₃); 2.16-2.91 (m, 4H); 6.55 (s, 2H, 3-H-Ind)); 6.78-8.12 (m, 20H);8.39-8.76 (m, 4H)

Synthesis ofrac-dimethylsilyl-bis{1-(2-i-butyl-4-(1-naphthyl)indenyl)}zirconiumdichloride 2-bromobenzylidene diethylmalonic acid

A 500-ml three-necked round flask (Dean & Stark) equipped with astirring bar, a Dimroth condenser and a thermometer was charged with74.0 g (400 mmol) of 2-bromobenzaldehyde, 70.48 g (440 mmol) ofdiethylmaloic acid, 1.6 ml of piperidine, 4.8 ml of acetic acid and 80ml of benzene. The mixture was subjected to azeotoropic dehydration for7 hours in an oil bath of 110° C. under a nitrogen atmosphere. After thereaction was completed, the reaction mixture was cooled to roomtemperature and 300 ml of ether was added, followed by washing with 100ml of water two times. The organic phase was dried over anhydrous Na₂SO₄. The solvent was concentrated under reduced pressure and theconcentrate of a orange liquid was distilled under reduced pressure toobtain 117.2 g of the desired product as a yellow liquid (yield: 90%).

bp.: 164°-171° C./0.2 mmHg

NMR (CDCl₃, 90 MHz): δ=1.17 (t, J=7.0 Hz, 3H, CH₃); 1.34 (t, J=7.0 Hz,3H, CH₃); 4.22 (q, J=7.0 Hz, 2H, --O--CH₂ --); 4.32 (q, J=7.0 Hz, 2H,--O--CH₂ --) 7.06-7.80 (m, 3H); 7.97 (s, 1H);

IR (Neat): 1725 cm⁻¹ (ν_(C)═O);

mp.: 43.6°-45.6° C.

Synthesis of 2-bromobenzyl diethylmalonic acid

A 500-ml three-necked round flask equipped with a stirrer, a droppingfunnel and thermometer was charged with 13.64 g (360.8 mmol) of sodiumborohydride and 280 ml of ethanol. To the mixture was added a solid of2-bromobenzylidene diethylmalonic acid in portions under a nitrogenatmosphere while cooling with ice bath. After the addition wascompleted, the mixture was further stirred for 1 hour. Then, theresulting white slurry was filtered, and the residue was washed with 50ml of ethanol. The combined filtrate was concentrated under reducedpressure, which was then extracted with 200 ml of water and 200 ml ofether. The organic phase was separated, and the aqueous phase wasfurther extracted with 200 ml of ether. The combined organic phase waswashed with 200 ml of a saturated NaCl aq. two times, followed by dryingover anhydrous Na₂ SO₄. The solvent was evaporated under reducedpressure. The residue was separated and purified with silica gelchromatography (eluting with hexane/ethyl acetate(6/1 parts by volume))to obtain 55.4 g of the desired product as a colorless liquid (yield:47%).

NMR (CDCl₃, 90 MHz): δ=1.21 (t, J=7.1 Hz, 6H, CH₃); 3.33 (d, J=7.6 Hz,2H); 3.84 (dd, J=7.6 Hz, 7.6 Hz, 1H); 4.13 (q, J=7.1 Hz, 4H, --O--CH₂--) 6.87-7.36 (m, 3H); 7.51 (dd, J=2.3 Hz, 7.6 Hz, 1H);

IR (Neat): 1730 cm⁻¹, 1750 cm⁻¹ (ν_(C)═O)

Synthesis of 3-(2-bromophenyl}-2-i-butylpropionic acid

A 1-liter four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 20.45 g(182.3 mmol) of potassium-t-butoxide, 180 ml of toluene and 25 ml ofN-methylpyrrolidone. To the mixture was added a solution containing 50.0g (151.9 mmol) of 2-bromobenzyl diethylmalonic acid dissolved in 40 mlof toluene at room temperature under a nitrogen atmosphere. After theaddition was completed, the temperature in the flask was elevated to 60°C. and the reaction mixture was stirred for 1 hour. Then, to theresulting mixture was added a solution containing 24.97 g (182.3 mmol)of i-butylbromide dissolved in 30 ml of toluene at the same temperature.After the addition was completed, the temperature was elevated and themixture was stirred under reflux for 18 hours. The reaction mixture waspoured onto 150 ml of a saturated aqueous solution of sodium chloride,and the mixture was adjusted to pH 3 with addition of 12% hydrochloricacid. The organic phase was separated, and the aqueous phase wasextracted with 100 ml of ether two times. The combined organic phase waswashed with 200 ml of a saturated aqueous solution of sodiumbicarbonate, and then 150 ml of a saturated aqueous solution of sodiumchloride, followed by drying over anhydrous Na₂ SO₄. The solvent wasconcentrated under reduced pressure to obtain 64 g of the concentrate asan orange liquid.

Then, a 1-liter four-necked round flask equipped with a stirrer, aDimroth condenser, a dropping funnel and a thermometer was charged with100 g (1.52 mol) of potassium hydroxide and 300 ml of an aqueousmethanol solution (methanol/water=4/1 (v/v)). To the mixture was addeddropwise the above-obtained concentrate at room temperature under anitrogen atmosphere. After the addition was completed, the temperaturewas elevated and the mixture was stirred under reflux for 7 hours. Afterthe reaction was completed, the methanol was evaporated under reducedpressure. The residue was dissolved in water and adjusted to pH 3 withaddition of dilute sulfuric acid. The precipitate was filtered andwashed with 150 ml of ether. The combined filtrate was separated to anoil phase and an aqueous phase. The aqueous phase was extracted with 100ml of ether two times. The combined organic phase was washed with 100 mlof a saturated aqueous solution of sodium chloride, followed by dryingover anhydrous Na₂ SO₄. The solvent was concentrated under reducedpressure to obtain 49.7 g of an orange-brown pasty liquid. Then, theabove-obtained orange-brown pasty liquid was charged into a 300-ml flaskequipped with a stirring bar and a Dimroth condenser, and heated to 180°C. and stirred for 1.5 hours under a nitrogen atmosphere. 42.1 g of thedesired product was obtained as a dark red pasty liquid (yield: 97%).This carboxylic acid was used in the next reaction without furtherpurification.

NMR (CDCl₃, 90 MHz): δ=0.90 (d, J=6.4 Hz, 3H, CH₃); 0.93 (d, J=6.4 Hz,3H, CH₃); 1.07-1.89 (m, 3H); 2.57-3.09 (m, 3H); 6.72-7.30 (m, 4H); 7.51(dd, J=2.0 Hz, 7.1 Hz, 1H);

Synthesis of 3-(2-bromophenyl)-2-i-butylpropionic acid chloride

A 200-ml four-necked round flask equipped with a stirring bar, a Dimrothcondenser, a hermometer and a NaOH trap was charged with 42.1 g of3-(2-bromophenyl)-2-i-butylpropinonic acid and 60 ml of thionylchloride. The mixture was stirred under reflux for 1.5 hour under anitrogen atmosphere. After the reaction was completed, the unreactedthionyl chloride was evaporated under reduced pressure. The residue wasdistilled under reduced pressure to obtain 40.3 g of the desired productas a pale orange liquid (yield: 90%).

bp.: 130°-132° C./0.1-0.2 mmHg

NMR (CDCl₃, 90 MHz): δ=0.90 (d, J=6.4 Hz, 3H, CH₃); 0.96 (d, J=6.4 Hz,3H, CH₃); 1.13-2.06 (m, 3H); 2.71-3.53 (m, 3H): 6.88-7.40 (m, 3H); 7.50(d, J=6.9 Hz, 1H);

IR (Neat): 1780 cm⁻¹ (ν_(C)═O)

Synthesis of 4-bromo-2-i-butyl-1-indanone

A 500-ml four-necked round flask equipped with a stirrer, a Dimrothcondenser, a dropping funnel, a thermometer and a NaOH trap was chargedwith 20.33 g (152.5 mmol) of anhydrous aluminum chloride and 70 ml ofcarbon disulfide. To the mixture was added dropwise a solutioncontaining 40.2 g (132.6 mmol) of the above-obtained3-(2-bromophenyl)-2-i-butylpropionic acid chloride dissolved in 50 ml ofcarbon disulfide under a nitrogen atmosphere while cooling with icebath. After the addition was completed, the temperature in the flask waselevated to room temperature, and the mixture was stirred for 1 hour.Then, the reaction mixture was quenched by pouring onto 200 ml of icewater, which was then extracted with 100 ml of ether three times. Thecombined organic phase was washed with 100 ml of a saturated aqueoussolution of sodium bicarbonate, and then 100 ml of a saturated NaCl aq.,followed by dried over anhydrous Na₂ SO₄. The solvent was evaporatedunder reduced pressure to give 37.4 g of the desired product as anorange liquid. This ketone was used in the next reaction without furtherpurification.

NMR (CDCl₃, 90 MHz): δ=0.99 (t, J=6.4 Hz, 6H, CH₃); 1.02-1.55 (m, 1H);1.59-2.12 (m, 2H); 2.53-2.94 (m, 2H): 3.02-3.62 (m, 1H); 7.24 (t, J=7.6Hz, 1H); 7.66 (d, J=7.6 Hz, 1H); 7.74 (d, J=7.6 Hz, 1H);

IR (Neat): 1718 cm⁻¹ (ν_(C)═O)

Synthesis of 4-bromo-2-i-butyl-1-hydroxyindane

A 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with2.51 g (66.3 mmol) of sodium boron hydride and 85 ml of ethanol. To themixture was added dropwise a solution containing 37.0 g (132.6 mmol) ofthe above-obtained 4-bromo-2-i-butyl-1-indanone dissolved in 55 ml ofethanol at room temperature under a nitrogen atmosphere. After theaddition was completed, the mixture was further stirred for 16 hours.Then, the reaction mixture was concentrated under reduced pressure,which was then extracted with 150 ml of water and 150 ml of ether. Theorganic phase was separated, and the aqueous phase was further extractedwith 100 ml of ether. The combined organic phase was washed with 100 mlof a saturated NaCl aq. two times, followed by dried over anhydrous Na₂SO₄. The solvent was evaporated under reduced pressure to obtain 34.4 gof the desired product (mixture of two isomers) as a pale yellow solid(yield: 96%). This alcohol was used in the next reaction without furtherpurification.

NMR (CDCl₃, 90 MHz): δ=0.76-1.23 (m, 6H, CH₃); 1.25-2.01 (m, 3H);2.05-3.36 (m, 3H); 4.80, 5.03 (each bs, total 1H, ##STR17## 6.89-7.57(m, 3H);

IR (KBr disk): 3232 cm⁻¹ (ν_(OH))

Synthesis of 4-bromo-2-i-butyl-1-trimethylsilyloxyindane

A 300-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with34.4 g (127.8 mmol) of 4-bromo-2-i-butyl-1-hydoxyindane, 23.1 ml (166.2mmol) of triethylamine and 118 ml of methylene chloride. To the mixturewas added dropwise 20 ml of a methylene chloride solution containing19.45 ml (153.4 mmol) of trimethylsilyl chloride under a nitrogenatmosphere while cooling with ice bath. After the addition wascompleted, the temperature was elevated to room temperature, and themixture was further stirred for 1.5 hours. The reaction mixture waspoured onto a mixture of 200 ml of ice water and 20 ml of a saturatedaqueous solution of sodium bicarbonate. Then, the organic phase wasseparated, and the aqueous phase was further extracted with 50 ml ofmethylene chloride two times. The combined organic phase was washed with100 ml of a saturated NaCl aq., followed by dried over anhydrous Na₂SO₄. The solvent was evaporated under reduced pressure. The residue wasdistilled under reduced pressure to obtain 41.8 g of the desired product(mixture of two isomers) as a pale yellow liquid (yield: 96%).

bp.: 141°-146° C./0.1-0.2 mmHg

NMR (CDCl₃, 90 MHz): δ=0.15-0.24 (each s, total 9H, Si--CH₃); 0.76-1.10(m, 6H, CH₃); 1.20-1.84 (m, 3H); 2.12-3.26 (m, 3H): 4.77, 5.06 (each bd,each J=6.4 Hz, total 1H, ##STR18## 6.88-7.44 (m, 3H)

Synthesis of 2-i-butyl-1-hydroxy-4-(1-naphtyl)indene

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with5.0 g (14.65 mmol) of 4-bromo-2-i-n-butyl-1-trimethylsilyloxyindane,53.6 mg (0.073 mmol) of PdCl₂ (dppf) and 15 ml of dry ether. To themixture was added dropwise 40.7 ml (29.3 mmol) of an ether/benzenesolution containing 0.72M 1-naphthylmagnesium bromide at roomtemperature under a nitrogen atmosphere. After the addition wascompleted, the temperature in the flask was elevated to 50° to 51° C.,and the mixture was stirred under reflux for 18 hours. After thereaction was completed, the temperature was cooled to room temperature.Thereafter, the reaction mixture was added to a mixture of 100 ml of asaturated aqueous solution of ammonium chloride and ice so as todecompose an excess amount of Grignard reagent. The resultant mixturewas extracted with 50 ml of ether two times. The combined organic phasewas washed with a saturated aqueous solution of sodium bicarbonate, andthen a saturated NaCl aq., followed by dried over anhydrous Na₂ SO₄. Thepalvent was evaporated to obtain 12.1 g of a pasty liquid.

Then, the above-obtained pasty liquid was diluted with 24.2 ml oftetrahydrofuran and 7 ml of 12% hydrochloric acid was added. The mixturewas stirred at room temperature for 3 hours. After the reaction wascompleted, the reaction mixture was added to 50 ml of a saturatedaqueous solution of sodium bicarbonate, which was then extracted with 50ml of ether two times. The combined organic phase was washed with asaturated aqueous solution of sodium bicarbonate, and then a saturatedNaCl aq., followed by dried over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure. The residue was separated andpurified with silica gel chromatography (eluting with hexane/ethylacetate(20/1 parts by volume)) to obtain 4.54 g of the desired product(mixture of two kinds of isomers) as a brown pasty liquid (yield: 98%).

NMR (CDCl₃, 90 MHz): δ=0.71-1.07 (m, 6H); 1.13-2.91 (m, 7H); 4.88, 5.07(each bs, total 1H, ##STR19## 7.12-8.01 (m, 10H):

IR (Neat): 3328 cm⁻¹ (ν_(C)═O)

Synthesis of 2-i-butyl-4-(1-naphthyl)indene

A 200-ml three-necked round flask equipped with a stirring bar, aDimroth condenser, a dropping funnel and a thermometer was charged with4.54 g (14.4 mmol) of 2-i-butyl-1-hydroxy-4-(1-naphthyl)indene, 5.13 g(50.8 mmol) of triethylamine, 0.10 g (0.82 mmol) of4-dimethylaminopyridine and 57.7 ml of methylene chloride. To themixture was added dropwise a solution containing 3.87 ml (33.8 mmol) ofmethanesulfonyl chloride dissolved in 7.7 ml of methylene chloride undera nitrogen atmosphere while cooling with ice bath. After the additionwas completed, the temperature was elevated to room temperature and themixture was further stirred for 3 hours. The reaction mixture was pouredonto 100 ml of water Thereafter, the organic phase was separated, andthe aqueous phase was extracted with 50 ml of methylene chloride. Theextracted organic phases were combined and washed with a saturated NaClaq., followed by dried over anhydrous Na₂ SO₄. The solvent wasevaporated under reduced pressure. The residue was separated andpurified with silica gel chromatography (eluting with hexane/ethylacetate (20/1 parts by volume)) to obtain 3.98 g of the desired product(mixture of two isomers) as a pale yellow pasty liquid (yield: 93%).

NMR (CDCl₃, 90 MHz): δ=0.86 (d, J=6.4 Hz, 6H, CH₃); 1.13-1.99 (m, 1H);2.24 (d, J=6.4 Hz, 2H); 3.01, 3.40 (each s, total 2H): 6.07, 6.55 (eachs, total 1H); 6.92-7.98 (m, 10H)

Synthesis of dimethylsilyl-bis 1-(2-i-butyl-4-(1-naphthyl)indene

A 100-ml three-necked flask equipped with a stirring bar, a Dimrothcondenser, a dropping funnel and a thermometer was charged with 2.37 g(7.95 mmol) of 2-i-buty-4-(1-napthyl)indene, 28 mg (0.22 mmol) of copperthiocyanate and 24 ml of absolute ether. To the mixture was addeddropwise 5.54 ml (8.75 mmol) of a hexane solution containing 1.58Mn-butyl lithium at room temperature under a nitrogen atmosphere. Afterthe addition was completed, the mixture was further stirred for 15hours. Then, to the reaction mixture was added dropwise a solutioncontaining 0.53 ml (4.37 mmol) of dimethyldichlorosilane dissolved in1.6 ml of dry ether. After the addition was completed, the mixture wasfurther stirred for 27.5 hours at room temperature. The reaction mixturewas filtered with Celite, and the filtrate was separated to an organicphase and an aqueous phase by addition of 30 ml of water. The organicphase was separated, and the aqueous phase was extracted with 30 ml ofether. The combined organic phase was washed with a saturated NaCl aq.,followed by dried over anhydrous Na₂ SO₄. The solvent was evaporatedunder reduced pressure to obtain a yellow pasty liquid residue. The thusobtained yellow pasty liquid residue was separated and purified withsilica gel chromatography (eluting with hexane/ethyl ether (160/1 partsby volume)) to obtain 1.85 g of the desired product (mixture of twoisomers) as a pale yellow solid (yield: 71%).

FD-MS: 653 (M⁺)

NMR (CDCl₃, 90 MHz): δ=-0.37 to -0.08 (m, 6H, Si--CH₃); 0.59-1.10 (m,12H, CH₃); 1.19-2.06 (m, 2H); 2.12-2.57 (m, 4H): 3.86, 3.95 (each bs,total 2H, ##STR20## 6.17, 6.26 (each bs, total 2H); 6.92-8.04 (m, 20H)

Synthesis ofrac-dimethylsilyl-bis{1-(2-i-butyl-4-(1-naphtyl)indenyl)}zirconiumdichloride

A 50-ml three-necked round flask equipped with a stirring bar, acondenser, a dropping funnel and thermometer was charged with 1.0 g(1.53 mmol) of dimethylsilyl-bis{1-(2-i-butyl-4-(1-naphthyl)indene)} and20 ml of dry ether. To the mixture was added dropwise 2.09 ml (3.22mmol) of a hexane solution containing 1.54M n-butyl lithium at roomtemperature. After the addition was completed, the mixture was furtherstirred for 15 hours. The resulting clear red reaction liquid was cooledto -68° C. To the solution was added 0.36 g (1.53 mmol) of ZrCl₄. Afterthe addition was completed, the mixture was allowed to warm to roomtemperature overnight under stirring. The resulting orange-yellowreaction slurry was filtered and washed with dry ether two times. To theresidue was added 25 ml of methylene chloride and the insoluble materialwas filtered off. The filtrate was concentrated to dryness at roomtemperature. The resulting orange-yellow dried material was dissolved in8 ml of methylene chloride, and the solution was concentrated to about1/2 of the total amount of the solution. To the solution was added 1 mlof dry ether, to give the precipitates which were filtered, and washedwith 1 ml of dry ether. The resulting solid was dried under reducedpressure to obtain 140 mg of an orange-yellow powder. NMR analysisshowed that this powder comprises a mixture of rac/meso (88/12). Then,the above-obtained powder was dissolved in 3 ml of methylene chloride.To the solution was added 6 ml of dry ether, to give the precipitateswhich were filtered, and washed with 0.5 ml of dry ether, followed bydried under reduced pressure to obtain 77 mg of the desired product as ayellow-orange powder (yield: 6%).

FD-MS: 812 (M⁺)

NMR (CDCl₃, 90 MHz): δ=0.71 (d, J=6.4 Hz, 6H, CH₃); 0.86 (d, J=6.4 Hz,6H, CH₃); 1.36 (s, 6H, Si--CH₃); 1.78-2.22 (m, 2H): 2.51-2.87 (m, 4H);6.41 (s, 2H, 3-H-Ind); 6.86-8.02 (m, 20H)

Example 14

The polymerization was carried out in the same manner as in Example 2except that therac-dimethylsilyl-bis{1-(2-ethyl-4-(phenantolyl)indenyl)}zirconiumchloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component, and the flow rate ofhydrogen was changed to 3 liters/hr.

The amount of the thus obtained polymer was 23.4 g and thepolymerization activity was 12.0 kg-PP/mmol-Zr·hr. The intrinsicviscosity η! was 2.92 dl/g, and Mw/Mn was 2.22. In the polymer, thetriad tacticity was 99.7%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.14%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was less than the detectablelower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 15

The polymerization was carried out in the same manner as in Example 2except that therac-dimethylsilyl-bis{1-(2-butyl-4-(1-naphthyl)indenyl)}zirconiumdichloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component, and the flow rate ofhydrogen was changed to 3 liters/hr.

The amount of the thus obtained polymer was 24.6 g and thepolymerization activity was 12.6 kg-PP/mmol-Zr·hr. The intrinsicviscosity R! was 3.05 dl/g, and Mw/Mn was 2.10. In the polymer, thetriad tacticity was 99.2%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.19%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was less than the detectablelower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 16

The polymerization was carried out in the same manner as in Example 2except that therac-dimethylsilyl-bis{1-(2-n-propyl-4-(1-naphthyl)indenyl)}zirconiumdichloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component, and the flow rate ofhydrogen was changed to 3 liters/hr.

The amount of the thus obtained polymer was 19.9 g and thepolymerization activity was 10.2 kg-PP/mmol-Zr·hr. The intrinsicviscosity η! was 3.13 dl/g, and Mw/Mn was 2.19. In the polymer, thetriad tacticity was 99.5%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.19%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was less than the detectablelower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 17

The polymerization was carried out in the same manner as in Example 2except that therac-dimethylsilyl-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconiumdichloride was used in place of therac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideas a transition metal compound catalyst component, and the flow rate ofhydrogen was changed to 3 liters/hr.

The amount of the thus obtained polymer was 14.5 g and thepolymerization activity was 7.4 kg-PP/mmol-Zr·hr. The intrinsicviscosity η! was 3.47 dl/g, and Mw/Mn was 2.15. In the polymer, thetriad tacticity was 99.7%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.16%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was less than the detectablelower limit (less than 0.03%).

The results are shown in Table 1 (I) and (II).

Example 18

A 2-liter autoclave throughly purged with nitrogen was charged with 920ml of hexane and 50 g of 1-butene. Then, to the autoclave was added 1mmol of triisobutylaluminum. After elevating the temperature of thereaction system to 70° C., propylene was fed to the system to a totalpressure of 7 kg/cm² -G. To the autoclave were added 0.28 mmol ofmethylaluminoxane and 7×10⁻⁴ mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-ethyl-4-phenyl-1-indenyl)}zirconiumdichloride to polymerize the monomers for 30 minutes while propylene wascontinuously fed to keep the total pressure of 7 kg//cm² -G. After thepolymerization, the autoclave was. released, the resulting polymer wasrecovered in a large amount of methanol, and dried at 110° C. for 12hours under reduced pressure.

The amount of the polymer obtained was 52.1 g. The polymerizationactivity was 149 kg-polymer/mmolZr·hr. The polymer had a 1-butenecontent of 20.2 mol %, an intrinsic viscosity η! of 1.90 dl/g, Mw/Mn of2.05 and a melting point of 101.5° C.

The results are shown in Table 1 (I) and (II).

Example 19

A 500-ml gas through type glass reactor throughly purged with nitrogenwas charged with 250 ml of toluene and 9.4 ml of 1-octene, followed byelevating the temperature of the reactor to 50° C. The system wassufficiently saturated by feeding propylene at a flow rate of 250liters/hr. Then, to the autoclave were added 0.1 mmol oftriisobutylaluminum, 1.1 mmol of methylaluminoxane and 0.002 mmol (interms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichlorideto polymerize the monomers for 30 minutes while propylene wascontinuously fed at a flow rate of 250 liters/hr to keep the temperaturein the system of 50° C. The polymerization was stopped by the additionof a small amount of methanol. The polymer solution was added to 2liters of methanol containing a small amount of hydrochloric acid toprecipitate a polymer. The precipitated polymer was recovered and driedunder reduced pressure at 110° C. for 12 hours.

The amount of the polymer obtained was 5.4 g. The polymerizationactivity was 5.4 kg-polymer/mmolZr·hr. The polymer had a 1-octenecontent of 6.7 mol %, an intrinsic viscosity η! of 1.44 dl/g, Mw/Mn of2.41 and a melting point of 131° C.

The results are shown in Table 1 (I) and (II).

Example 20

A 200-ml reactor equipped with stirring blade throughly purged withnitrogen was charged with 80 liters of hexane, 80 mmol oftriisobutylaluminum, 0.25 liter of hydrogen, 9 kg of ethylene and 0.3 kgof propylene, followed by elevating the temperature of the reactor to70° C. Then, to the reactor were added 18 mmol of methylaluminoxane and0.06 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichlorideto polymerize at 70° C. for 30 minutes. During the polymerization, 13.7kg of propylene and 0.5 kg of ethylene were respectively fed to thereactor. After the polymerization, the autoclave was released, theresulting polymer was recovered in a large amount of methanol, and driedat 80° C. for 10 hours under reduced pressure.

The amount of the polymer obtained was 7.0 kg. The polymerizationactivity was 117 kg-polymer/mmolZr·hr. The polymer had an ethylenecontent of 4.7 mol % and an intrinsic viscosity η! of 2.7 dl/g. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 97.5%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.22%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.05%.

The results are shown in Table 1 (I) and (II).

The film of the copolymer had a heat seal-starting temperature of 120°C. and a heat seal-starting tempeature after heat treatment of 123° C.

The results are shown in Table 2.

Example 21

A 2-liter autoclave throughly purged with nitrogen was charged with 900ml of hexane. Then, to the autoclave was added 1 mmol oftriisobutylaluminum. After elevating the temperature of the reactionsystem to 70° C., ethylene was fed to the system to keep a pressure of1.5 kg/cm² -G, and then propylene was fed to the system to keep a totalpressure of 8 kg/cm² -G. To the autoclave were added 0.3 mmol ofmethylaluminoxane and 0.001 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-dimethyl-4-phenylindenyl)}zirconiumdichloride to polymerize the monomers for 7 minutes while propylene wascontinuously fed to keep the total pressure of 8 kg//cm² -G. After thepolymerization, the autoclave was released, the resulting polymer wasrecovered in a large amount of methanol, and dried at 110° C. for 10hours under reduced pressure.

The amount of the polymer obtained was 25.4 g. The polymerizationactivity was 25 kg-polymer/mmolZr·hr. The polymer had an ethylenecontent of 2.5 mol % and an intrinsic viscosity η! of 3.1 dl/g. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 97.6%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.22%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.05%.

The results are shown in Table 1 (I) and (II).

The film of the copolymer had a heat seal-starting temperature of 134°C. and a heat seal-starting tempeature after heat treatment of 134° C.

The results are shown in Table 2.

Example 22

A 17-liter autoclave throughly purged with nitrogen was charged with 8liters of hexane. After the temperature of the reaction system waselevated to 60° C., propylene and ethylene were continuously fed to thesystem at a flow rate of 250 liters/hr and a flow rate of 170 liters/hr,respectively, to elevate the pressure to 8 kg/cm² -G.

Then, to the autoclave were added 8 mmol of triisobutylaluminum, 1.8mmol of methylaluminoxane and 0.006 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-dimethyl-4-phenylindenyl)}zirconiumdichloride to polymerize the monomers at 60° C. for 45 minutes while amixed gas of propylene and ethylene (mol ratio: 60/40) were continuouslyfed to keep the pressure of 8 kg//cm² -G. After the polymerization, theautoclave was released, the resulting polymer was recovered in a largeamount of methanol, and dried at 110° C. for 10 hours under reducedpressure.

The amount of the polymer obtained was 860 g. The polymerizationactivity was 143 kg-polymer/mmolZr·hr. The polymer had an ethylenecontent of 33.6 mol % and an intrinsic viscosity η! of 1.4 dl/g. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 97.5%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.27%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.03%.

The results are shown in Table 1 (I) and (II).

The copolymer had an izod impact strength of 30 kg·cm/cm, a film impactstrength of 5300 kg·cm/cm and MFR of 17.8 g/10 min.

The results are shown in Table 2.

Example 23

The polymerization was carried out in the same manner as in Example 22except that the feed of ethylene was changed to 60 liters from 170liters, and the mol ratio of propylene to ethylene in the mixed gas waschanged to 81/19 from 60/40.

The amount of the polymer obtained was 900 g. The polymerizationactivity was 150 kg-polymer/mmolZr·hr. The polymer had an ethylenecontent of 15.4 mol % and an intrinsic viscosity η! of 1.5 dl/g. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 96.7%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.28%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.03%.

The results are shown in Table 1 (I) and (II).

The film of the copolymer had a heat seal-starting temperature of 80° C.and a heat seal-starting temperature after heat treatment of 83° C.

The results are shown in Table 2.

Example 24

A 17-liter autoclave throughly purged with nitrogen was charged with 8liters of hexane and 40 ml of hydrogen. After the temperature of thereaction system was elevated to 70° C., propylene and ethylene werecontinuously fed to the system at a flow rate of 253 liters/hr and aflow rate of 22 liters/hr, respectively, to elevate the pressure to 6.5kg/cm² -G.

Then, to the autoclave were added 8 mmol of triisobutylaluminum, 1.8mmol of methylaluminoxane and 0.006 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-dimethyl-4-phenylindenyl)}zirconiumdichloride to polymerize the monomers at 70° C. for 30 minuets while amixed gas of propylene and ethylene (mol ratio: 92/8) was continuouslyfed to keep the pressure of 6.5 kg//cm² -G. After the polymerization,the autoclave was released, the resulting polymer was recovered in alarge amount of methanol, and dried at 110° C. for 10 hours underreduced pressure.

The amount of the polymer obtained was 700 g. The polymerizationactivity was 117 kg-polymer/mmolZr·hr. The polymer had an ethylenecontent of 6.0 mol % and an intrinsic viscosity η! of 2.0 dl/g. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 97.5%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.18%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.03%.

The results are shown in Table 1 (I) and (II).

The film of the copolymer had a heat seal-starting temperature of 112°C. and a heat seal-starting temperature after heat treatment of 115° C.

The results are shown in Table 2.

                  TABLE 1 (I)                                                     ______________________________________                                        Comonomer                 Polymerization                                                  Content  Yield    Activity  η!                                Kind        (%)      (g)      *1       (dl/g)                                 ______________________________________                                        Ex. 2  --       --       51.3   4.02     3.37                                 Ex. 3  --       --       60.7   31.1     3.01                                 Comp.                                                                         Ex. 1  --       --       4.7    2.4      4.05                                 Ex. 4  ethylene 3.9      5.62   33.7     1.80                                 Ex. 5  ethylene 8.7      6.63   39.8     1.66                                 Ex. 6  ethylene 28.9     8.95   53.7     1.34                                 Ex. 8  --       --       20.2   10.4     3.08                                 Ex. 9  ethylene 7.9      2.08   12.5     1.39                                 Ex. 14 --       --       23.4   12.0     2.92                                 Ex. 15 --       --       24.6   12.6     3.05                                 Ex. 16 --       --       19.9   10.2     3.13                                 Ex. 17 --       --       14.5   7.4      3.47                                 Ex. 18 1-butene 20.2     52.1   149      1.90                                 Ex. 19 1-octene 6.7      5.4    5.4      1.44                                 Ex. 20 ethylene 4.7      7000   117      2.7                                  Ex. 21 ethylene 2.5      25.4   25       3.1                                  Ex. 22 ethylene 33.6     860    143      1.4                                  Ex. 23 ethylene 15.4     900    150      1.5                                  Ex. 24 ethylene 6.0      700    117      2.0                                  ______________________________________                                         *1:kg-polymer/mmol-Zr.hr                                                 

                  TABLE 1 (II)                                                    ______________________________________                                                    Proportion of inversely                                                       inserted units                                                                  2,1-insertion                                                                            1,3-insertion                                        mm Fraction   (%)        (%)       Mw/Mn                                      ______________________________________                                        Ex. 2   99.7      0.10       <0.03   2.22                                     Ex. 3   99.5      0.15       <0.03   2.18                                     Comp.                                                                         Ex. 1   98.6      0.33       <0.03   2.18                                     Ex. 4   99.3      0.12       <0.03   2.15                                     Ex. 5   99.2      0.12       <0.03   2.46                                     Ex. 6   98.5      0.09       <0.03   1.95                                     Ex. 8   99.7      0.12       <0.03   2.09                                     Ex. 9   99.2      0.10       <0.03   2.33                                     Ex. 14  99.7      0.14       <0.03   2.22                                     Ex. 15  99.2      0.19       <0.03   2.10                                     Ex. 16  99.5      0.19       <0.03   2.19                                     Ex. 17  99.7      0.16       <0.03   2.15                                     Ex. 18  --        --         --      2.05                                     Ex. 19  --        --         --      2.41                                     Ex. 20  97.5      0.22       <0.05   --                                       Ex. 21  97.6      0.22       <0.05   --                                       Ex. 22  97.5      0.27       <0.03   --                                       Ex. 23  96.7      0.28       <0.03   --                                       Ex. 24  97.5      0.18       <0.03   --                                       ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                             Heat                                                                          seal-                MFR of                                                   starting      IZ of  composi-                                        Heat     tempera-      composi-                                                                             tion                                            seal-    ture   Film   tion with                                                                            with                                     Melt-  starting after  impact polypro-                                                                             polypro-                            Ex-  ing    tempera- heat   strength                                                                             pylene pylene                              am-  point  ture     treatment                                                                            (kg · cm/                                                                   (kgf · cm/                                                                  (g/10                               ple  (°C.)                                                                         (°C.)                                                                           (°C.)                                                                         cm)    cm)    min)                                ______________________________________                                        Ex. 4                                                                              126    129      132    --     --     --                                  Ex. 5                                                                              105    106      109    --     --     --                                  Ex. 6                                                                              --     --       --     5300   28     --                                  Ex. 9                                                                              109    106      110    --     --     --                                  Ex.  123    120      123    --     --     --                                  20                                                                            Ex.  137    134      134    --     --     --                                  21                                                                            Ex.  --     --       --     5300   30     17.8                                22                                                                            Ex.   78     80       83    --     --     --                                  23                                                                            Ex.  115    112      115    --     --     --                                  24                                                                            ______________________________________                                    

What is claimed is:
 1. A process for propylene polymerization comprisingpolymerizing propylene or copolymerizing propylene and at least one kindof α-olefin selected from the group consisting of ethylene and α-olefinsof 4 to 10 carbon atoms to obtain propylene homopolymer or propylenecopolymer containing propylene units in an amount of not less than 50%by mol in the presence of a propylene polymerization catalyst selectedfrom the group consisting of(I) a propylene polymerization catalystproduced by contacting, in any order,(A) a propylene polymerizationcatalyst component comprising a transition metal compound represented bythe following formula (I): ##STR21## M is a transition metal selectedfrom the group consisting of zirconium and hafnium; R¹ is a hydrocarbongroup of 2 to 6 carbon atoms; R² is an aryl group selected from thegroup consisting of anthracenyl and phenanthryl, which may besubstituted with a hydrocarbon group of 1 to 20 carbon atoms; X¹ and X²are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group or a sulfur-containing group; and Y is adivalent silicon-containing group selected from the group consisting ofdialkylsilylene, alkylarylsilylene and diarylsilylene; with (B) at leastone compound selected from the group consisting of(B-1) an aluminoxane,and (B-2) a compound which reacts with said transition metal compound toform an ion pair; (II) a propylene polymerization catalyst produced bycontacting, in any order,said propylene polymerization catalystcomponent as defined in (A) above, said at least one compound as definedin (B) above, and (C) an organoaluminum compound; (III) a propylenepolymerization catalyst produced by contacting, in any order,a fineparticle carrier, said propylene polymerization catalyst component asdefined in (A) above, and said at least one compound as defined in (B)above, wherein said propylene polymerization catalyst as defined in (A)above and said at least one compound as defined in (B) above aresupported on said fine particle carrier; (IV) a propylene polymerizationcatalyst produced by contactingsaid propylene polymerization catalyst asdefined in (III) above, with an organoaluminum compound as defined in(C) above; (V) a propylene polymerization catalyst produced byprepolymerizing propylene with said propylene polymerization catalyst asdefined in (IV) above; and (VI) a propylene polymerization catalystproduced by contactingsaid propylene polymerization catalyst as definedin (V) above, with an organoaluminum compound as defined in (C) above.2. The process for olefin polymerization a claimed in claim 1, whereinin formula (I)X¹ and X² are each a halogen atom; and Y is a di-C₁ -C₃-alkyl silyl group.
 3. The process for olefin polymerization as claimedin claim 1, wherein M is zirconium, X¹ and X² are each methyl and Y is adimethylsilyl group.
 4. The process for olefin polymerization as claimedin claim 3, wherein R¹ is ethyl.